CN105713585B - Full oil base drilling fluid and preparation method thereof - Google Patents
Full oil base drilling fluid and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of full oil base drilling fluids and preparation method thereof, mainly solve the problems, such as that emulsion droplet and organic soil particle in oil base drilling fluid in the prior art cause unconventional low pressure and low permeability, water sensitivity and water phase activity difference big and the damage for easily causing solid phase damage stratum and oil base drilling fluid are to water enchroachment (invasion) poor resistance, the present invention by terms of weight fraction including following components: (1) 100 parts of base oil；It (2) include that the compound emulsifying agent of primary emulsion (I) and coemulsifier (II) is no less than 0.5 part；(3) 0.1~5 parts of tackifier；(4) 0.5~5 parts of fluid loss additive；The full oil base drilling fluid of (5) 0~5 parts of alkaline matter and the technical solution of preparation method, the problem is preferably resolved, can be used for the drilling completion production technology that unconventional low pressure and low permeability, water sensitivity and water phase activity difference are big and solid phase is easily caused to damage oil-gas stratigraphic deposits.
Description
Technical field
The present invention relates to a kind of full oil base drilling fluids and preparation method thereof, are suitable for unconventional low pressure and low permeability, water sensitivity
And water phase activity difference is big and easily causes the brill well-completing process of solid phase damage oil-gas stratigraphic deposits.
Background technique
As the continuous reduction and exploitation of petroleum reserves are difficult, countries in the world are increased one after another to bad ground petroleum resources
The investment of exploration and development develops an urgent demand that new oil reservoir has become current each major oil companies' development.At present both at home and abroad
Oil field, especially domestic elephant subsequently entered development late stage, gradually started to employ some low pressure and low permeability oil reservoirs, water sensitivity
And water phase activity difference is big and solid phase damages the exploration and developments of serious oil-gas stratigraphic deposits.The exploitation difficulty of these oil-gas reservoirs
Greatly, drilling fluid density is required high.Drilling fluid leakage and protection oil-gas Layer in order to prevent, it is often necessary to which the density of drilling fluid is low
In 1.0g/cm3.The system for meeting this needs at present is all with gas, oil mutually for density palliative.Aerated mud or foam
Drilling fluid has compressibility since there are many deficiencies for it, and pulse signal decaying is serious, and horizontal well drilling, extended reach well need
It to use when MWD and limit its use.In low-pressure low-permeability reservoir, emulsified water, cream are more or less contained in conventional oil base drilling fluid
The presence for changing water droplet will lead to reservoir and more serious water lock occur.
Oil base drilling fluid has stronger anti-collapse inhibition, lubricity and good reservoir protection performance, can especially 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.Often
The oil base drilling fluid of rule is generally water in oil emulsion drilling fluid, and it is living to balance water flooding that water phase therein often uses calcium chloride brine
Degree, prevents water enchroachment (invasion), water in oil emulsion drilling fluid (aqueous phase content is l0%~40%) have excellent greasy property, strong inhibition capability,
The advantages that borehole wall stability and good heat-resisting property, although being used widely at present, there are still certain deficiencies, such as drilling fluid
Containing a large amount of emulsification water droplets, plastic viscosity is high, influences rate of penetration, and reservoir emulsion droplet is caused to block；To keep Water-In-Oil
Emulsion intercalation method has used a large amount of emulsifiers, and will lead to rock surface from hydrophilic becomes oleophylic, causes formation damage；Drilling well
Liquid water phase activity is difficult by adjusting at any time to balance the activity of water in different stratum of easily collapsing, therefore cannot ensure various easily to collapse ground
Layer does not cause aquation and makes borehole well instability etc..Therefore be not suitable for that unconventional low pressure and low permeability, water sensitivity be strong and water phase activity difference
Brill well-completing process that is big and easily causing solid phase damage oil-gas stratigraphic deposits.And anhydrous non-clay full oil base drilling fluid is not aqueous, cream
Agent dosage is few, and also without the equilibrium problem for considering drilling fluid water phase activity and stratum water activity, thus full oil base drilling fluid removes
Have the advantages that also overcome above-mentioned deficiency outside water in oil emulsion drilling fluid.It can be used for easily collapse stratum, saline bed, especially water
The low-pressure stratum and ocean deepwater drilling on stratum and energy decline that phase activity differs greatly.
At present for the problem that the research and development of this respect, rock is taken due to not can solve, is full oil base drilling well argillaceous mostly
Liquid, if CN101215461 reports a kind of complete-oil synthetic base drilling fluid, the emulsifier used is Long carbon chain fatty acid amide, length
One of alkyl chain length benzene sulfonic acid calcium, polyolefin carboxylic acid ester or a variety of mixtures, although there is low toxicity, environmental protection, to reservoir
It injures the advantages that small, but it contains organoclay, solid phase is easily caused to damage, and preparation cost is high, limits its popularization and use.It is even
See the report of non-clay full oil base drilling fluid, but the water resistant of its system is invaded poor with the ability of salt contamination, also limits its popularization
It uses.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 into
Row meets low pressure and low permeability oil reservoir, water sensitivity by force and water phase activity difference is big and solid phase is damaged serious oil-gas stratigraphic deposits exploration and opened
The full oil base drilling fluid system of hair, of the present invention is exactly in this case, to be suitable for the full oil base drilling fluid on such stratum.
Summary of the invention
The first technical problem to be solved by the present invention is emulsion droplet and organoclay in oil base drilling fluid in the prior art
Particle causes the damage that unconventional low pressure and low permeability, water sensitivity are strong and water phase activity difference is big and solid phase is easily caused to damage stratum
Problem, this can be solved the problems, such as by providing a kind of full oil base drilling fluid, and it is special to meet such oil-gas stratigraphic deposits conventional drilling, big displacement
The special requirements such as well, seaborne horizontal well.
The second technical problem to be solved by the present invention is to provide the corresponding full oil of one of one kind and solution technical problem
The preparation method of base drilling fluid.
One of in order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of full oil base drilling fluid, packet
Include following components:
(1) 100 part of base oil；
It (2) 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；
(3) 0.1~5 parts of tackifier；
(4) 0.5~5 parts of fluid loss additive；
(5) 0~5 parts of alkaline matter；
Wherein, the primary emulsion is selected from least one of structure shown in logical formula (I), and coemulsifier is selected from general formula
(II) at least one of structure shown in；In mass, the ratio of the primary emulsion and coemulsifier meets 0 < auxiliary cream
Agent: primary emulsion≤1；
In general formula, R1For containing C8~C30Saturation or unsaturated alkyl, R2For hydrogen or R3CO, R3For C8~C30Saturation or not
The alkyl of saturation, x=1~10, y=1~40, z=0~40；R4For C7~C25Aliphatic group, R5And R6It is independently chosen from H, C2
~C4One of hydroxyalkyl.
In above-mentioned technical proposal, the dosage of the compound emulsifying agent, with the quality of contained primary emulsion and coemulsifier
Meter, preferably 0.5~5 part；R1、R3Preferably C11~C23Saturation or unsaturated hydrocarbons or C11~C23Saturated hydrocarbons and unsaturation
The mixing alkyl of hydrocarbon, R1、R3More preferably carbon atom number be 11,13,15,17,19,21 saturated hydrocarbons or
Unsaturated alkyl or 11,13,15,17,19,21 saturated hydrocarbons and unsaturated hydrocarbons mixing alkyl；X is excellent
It is selected as 2~6, more preferably 2 or 3；Y is preferably 1~20, and more preferably 1~10；Z is preferably 0~30, and more preferably 0~20；
The R4Preferably C11~C23Saturated hydrocarbyl or unsaturated alkyl；R5And R6Independent is preferably H, ethoxy, in hydroxypropyl
One kind, further preferably R5And R6Independent is preferably one of H, ethoxy, more preferably R5And R6Common preferably H,
One of ethoxy.
In above-mentioned technical proposal, the base oil be preferably one of white oil, synthetic oil, atoleine or more than one
Mixture；Alkaline matter is preferably lime powder；Tackifier are preferably butadiene rubber, butadiene-styrene rubber, EP rubbers, poly- first
One of base alkyl acrylate or more than one mixture；Fluid loss additive is preferably the modified rotten plant of long-chain organic amine
Acid, chain length are preferably C12、C16、C18。
In above-mentioned technical proposal, the primary emulsion can be further preferably from two kinds or two kinds in structure shown in (I)
Above mixture.
In above-mentioned technical proposal, the coemulsifier can be further preferably from two kinds or two in structure shown in (II)
Kind or more mixture.
In above-mentioned technical proposal, in mass, the ratio of the primary emulsion and coemulsifier is most preferably to assist cream
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, linolenic acid amide, stearic amide, lauric acid monoethanol
Amide, myristic acid single ethanol amide, palmitic monoethanolamide, palmitoleic acid single ethanol amide, oleic monoethanolamide, Asia
One of oleic monoethanolamide, linolenic acid single ethanol amide, stearic acid monoethanolamide or two kinds or more of mixture；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 known to the technical staff of field or biodiesel are raw material and corresponding amidation reagent progress amidation process
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
It anticipates one kind, can be any one in well known preparation method disclosed in document before this.
Key problem in technology of the invention is the selection of emulsifier, all polymer such as butadiene-styrene rubber, EP rubbers, poly- methyl
Alkyl acrylate is all substance commonly used in the art, and various polymer are preferably number-average molecular weight 1~10,000,000, more preferably
Number-average molecular weight 1~1,000,000.The preferred polymethylacrylic acid C of polyalkyl methacrylate12~C18Arrcostab.
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..
In above-mentioned technical proposal, the full oil base drilling fluid does not more preferably include oil base well-known to those skilled in the art
Drilling fluid usual component organoclay.
In above-mentioned technical proposal, the primary emulsion can be further preferably from two or more in structure shown in (I)
Mixture can play preferable synergistic effect.
In above-mentioned technical proposal, the coemulsifier can be further preferably from two or more in structure shown in (II)
Mixture, preferable synergistic effect can be played.
In above-mentioned technical proposal, the full oil base drilling fluid is more preferably wrapped with contained oil phase and water phase volume total volume meter
Include the water of 0-10%.
To solve above-mentioned technical problem two, the technical solution adopted in the present invention is as follows:
A kind of preparation method of full oil base drilling fluid, comprising the following steps:
(a)R1CONH(CH2)xNR2CH2CH2The preparation of OH (i.e. fatty acyl hydroxyethyl diamines)
R in the presence of basic catalyst1COOCH3(i.e. fatty acid methyl ester) and NH2(CH2)xNHCH2CH2OH (i.e. ethoxy
Diamines) 80~220 DEG C at a temperature of react 2~24 hours, preferred vacuum distillation removes unreacted raw material after reaction
The fatty acyl hydroxyethyl diamines is obtained with the methanol of generation.Wherein, the molar ratio of fatty acid methyl ester and hydroxyethyl diamine is
It is preferred that 1:0.1~6.The preferred potassium hydroxide of the basic catalyst, sodium hydroxide；The catalyst amount preferably accounts for fatty acid
The 0.01~10% of methyl esters quality.
(b)R1CONH(CH2)xNR2(CH2CH2O)y-(CH2CHCH3O)zThe system of H (i.e. fatty acyl group diamines Polyoxyalkylene ethers)
It is standby:
In the presence of basic catalyst, fatty acyl hydroxyethyl diamines synthesized by step (a) and required ethylene oxide
Or propylene oxide is 80~180 DEG C in reaction temperature, pressure is reacted to obtain the rouge under the conditions of being less than 0.80MPa gauge pressure
Fat acyl group diamines Polyoxyalkylene ethers.At least one of the basic catalyst preferably calcium hydroxide, calcium oxide.Catalyst amount is excellent
It is selected as the 0.5~6.0% of fatty acyl hydroxyethyl diamines quality.
(c) preparation of compound emulsifying agent:
By the fatty acyl hydroxyethyl diamines that step (a) obtains and/or the fatty acyl group that step (b) obtains
Diamines Polyoxyalkylene ethers and the coemulsifier are uniformly mixed in the ratio, obtain the oil base drilling fluid composite emulsifying
Agent；
(d) preparation of full oil base drilling fluid
The compound emulsifying agent that step (c) obtains is mixed with base oil, the alkaline matter, tackifier, fluid loss additive
Uniformly, the full oil base drilling fluid is obtained.
In above-mentioned technical proposal, a) the reaction temperature preferred scope in step be 100~200 DEG C, more preferably 120~
180℃；Catalyst is preferably alkali metal hydroxide or alkaline earth metal hydroxide, more preferably potassium hydroxide, and dosage is preferred
For account for fatty acid methyl esters monomer mass 0.5~5.0%；The molar ratio of fatty acid methyl ester and hydroxyethyl diamine is preferably 1~
2:1；Reaction time is preferably 6~16 hours.B) it is to account for fatty acyl hydroxyethyl two that catalyst amount, which is preferably catalyst amount,
The 1~5.0% of amine quality.
Full oil base drilling fluid prepared by the present invention, since the compound emulsifying agent used makes it have good heat-resistant salt-resistant
Can, so that the full oil base drilling fluid has excellent high-temperature stability.The full oil base drilling fluid heatproof is greater than 150 DEG C, API
Filter loss≤10ml, emulsion-breaking voltage >=2000V, water resistant are invaded up to 30%, and salt resistance invades 20%, are that a kind of heat resistance is excellent, leak-off
Measure full oil base drilling fluid system small, that stability is good.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
(a) synthesis (x=2) of N, N '-stearic bicine diester base hydroxyethyl ethylenediamine
49 parts of N-hydroxyethyl-ethylenediamine, 2.7 parts of KOH are added to equipped with sealing machine stirring, thermometer, the condensation of straight type
It manages, in the reactor of receiving flask, after 145 DEG C are stirred 1 hour, is slowly added dropwise in 270 parts of methyl stearate, 1 hour and drips
Finish.It is reacted 12 hours at 165 DEG C, the methanol generated in reaction is collected into receiving flask by condenser west tube.Decompression is steamed
Remaining low boiling point product and reaction raw materials are distillated, target product N, N '-stearic bicine diester base hydroxyethyl ethylenediamine are obtained.
(b) synthesis of N, N '-stearic bicine diester base hydroxyethyl ethylenediamine polyethenoxy ether (y=1, z=10)
203 grams of N, N '-stearic bicine diester base hydroxyethyl ethylenediamine and 185.4 parts of propylene oxide are in 7.6 parts of calcium oxide and hydrogen-oxygen
Change and reacts to obtain N, N '-stearic bicine diester base in 150 DEG C under the action of calcium compound (calcium oxide and calcium hydroxide weight ratio be 1:1)
348.5 parts of dihydroxy ethyl ethylenediamine polyethenoxy ether (y=1, z=10), molar yield 87.7%.
(c) preparation of oil base drilling fluid compound emulsifying agent
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 full oil base drilling fluid
Weigh 5 grams of the compound emulsifying agent of oil base drilling fluid that step (c) obtains, stainless steel is added in measurement 200mL5# white oil
Height stirs in cup, high-speed stirred 20min, sequentially adds 6 grams modified of humic acid of lauryl amine, EP rubbers (number-average molecular weight 5
Ten thousand) with 6 grams and 3 grams of CaO powder of polymethylacrylic acid cetyl ester (number-average molecular weight 500,000) mixture, continue high-speed stirred
20min obtains stable full oil base drilling fluid system.According to " GB/T 16782-1997 oil base drilling fluid On-Site Test Procedure "
Rheological parameter, emulsion-breaking voltage and the API filtration of the drilling fluid system are measured respectively.Wherein rheological parameter is sensible using Qingdao sea
The fast rotational viscometer of the ZNN-D6 type six of special instrument factory measures at 50 DEG C, and calculates modeling according to formula (1), (2) and (3)
Property viscosity (PV), yield value (YP) and ratio of dynamic shear force/yield value to plastic viscosity (YP/PV)；Emulsion-breaking voltage (ES) by the sensible special instrument factory in Qingdao DWY-2
Type drilling fluid electrical stability analyzer measures at 50 DEG C, and API filtration is measured by the multi-joint filtration device of SD type, and according to formula
(4) filter loss (FL) is calculated.The results are 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=(FL30min﹣ FL7.5min)×2(mL)
[embodiment 2]
(a) preparation (x=3) of N, N '-bis- erucic acid acyl group ethoxy propane diamine
47.13 parts, KOH5.6 parts of N- ethoxy propane diamine are added to cold equipped with sealing machine stirring, thermometer, straight type
It is solidifying to manage, in the reactor of receiving flask, after 150 DEG C are stirred 1 hour, slowly it is added dropwise in 281.3 parts of methyl erucate, 1 hour and is added dropwise
It finishes.Stop after being reacted 10 hours at 170 DEG C, the methanol generated in reaction is collected into receiving flask by condenser west tube
In.Remaining low boiling point product and reaction raw materials are evaporated under reduced pressure out, target product N, N '-bis- erucic acid acyl group ethoxy are obtained
Propane diamine.
(b) synthesis of N, N '-bis- erucic acid acyl group ethoxy propane diamine polyoxyethylene poly-oxygen propylene aether (y=10, z=20)
The N that step (a) is synthesized, N ' -320 parts, 9.6 parts calcium oxide of bis- erucic acid acyl group ethoxy propane diamine and hydroxide
(calcium oxide and calcium hydroxide weight ratio are added for 1:1) equipped with condensing unit, agitating device and gas distributor calcium compound
In high-pressure reactor, when being heated to 135 DEG C in logical nitrogen, 20 parts of water is added, are stirred to react 1 hour.After removing moisture, cooling
To 80 DEG C, high activity, highly selective compound oxidizing is made in the sulfuric acid (20wt%) that catalyst neutralisation theoretical amount is slowly added dropwise
System temperature is heated to 80 DEG C, opens vacuum system, be dehydrated 2 under a high vacuum by calcium alkoxylating catalyst reaction solution system
Hour, it is then purged 3 times with nitrogen, system reaction temperature is adjusted to 180 DEG C and is slowly passed through 167.1 parts of ethylene oxide, control pressure
Power≤0.60MPa.After reacting ethylene oxide is complete, 489.4 parts of propylene oxide are added, the reaction was continued in 180 DEG C, and reaction terminates
Afterwards, system is purged with nitrogen, is neutralized after cooling, dehydration, obtain N, N '-bis- erucic acid acyl group ethoxy propane diamine polyoxyethylene is poly-
845.7 parts of oxypropylene ether (y=10, z=20), molar yield 85.6%.
(c) preparation of oil base drilling fluid compound emulsifying agent
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 anhydrous non-clay full oil base drilling fluid
Weigh 8 grams of the oil base drilling fluid compound emulsifying agent that step (c) obtains, measurement 200mL5# white oil enters stainless steel height
It stirs in cup, high-speed stirred 20min, sequentially adds 3 grams modified of humic acid of cetylamine, butadiene rubber (number-average molecular weight 180,000)
3 grams and 4.5 grams of CaO powder, continues high-speed stirred 20min, obtain stable full oil base drilling fluid system.With [embodiment 1] (d)
The performance of measurement system, the results are shown in Table 1.
[embodiment 3]
(a) synthesis (x=3) of N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine
55.3 parts of N- ethoxy propane diamine, 8.33 parts of KOH are added to cold equipped with sealing machine stirring, thermometer, straight type
It is solidifying to manage, in the reactor of receiving flask, after 150 DEG C are stirred 1 hour, methyl soyate is slowly added dropwise (with quality percentage
Content meter, methyl soyate include following components: tetradecanoic acid formicester 0.557%, palmitinic acid formicester 18.250%, palm fibre
Palmitic acid olefin(e) acid formicester 1.402%, stearic acid methyl ester 5.495%, oleic acid formicester 30.203%, linoleic acid formicester 36.000%, flax
Sour formicester 3.587%, surplus other.) 277.6 parts, it is added dropwise in 1 hour.It reacts 8 hours at 165 DEG C, is generated in reaction
Methanol be collected into receiving flask by condenser west tube.Remaining low boiling point product and reaction raw materials are evaporated under reduced pressure out,
Obtain target product N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine.
(b) conjunction of N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine polyoxyethylene poly-oxygen propylene aether (y=3, z=5)
At
The N that step (a) is synthesized, N ' -256 parts, 15.4 parts calcium oxide of bis- vegetable oil acids acyl group ethoxy propane diamine and hydrogen
Aoxidizing calcium compound, (calcium oxide and calcium hydroxide weight ratio are added for 1:1) equipped with condensing unit, agitating device and gas dispersion
In the high-pressure reactor of device, when being heated to 135 DEG C in logical nitrogen, 20 parts of water is added, are stirred to react 1 hour.After removing moisture,
80 DEG C are cooled to, high activity, highly selective compound is made in the sulfuric acid (20wt%) that catalyst neutralisation theoretical amount is slowly added dropwise
System temperature is heated to 90 DEG C, opens vacuum system, take off under a high vacuum by calcium oxide alkoxylating catalyst reaction solution system
It water 2 hours, is then purged 3 times with nitrogen, system reaction temperature is adjusted to 160 DEG C and is slowly passed through 34.9 parts of ethylene oxide, controlled
Pressure≤0.60MPa.After reacting ethylene oxide is complete, 114.8 parts of propylene oxide are added, the reaction was continued in 160 DEG C, reaction knot
Shu Hou purges system with nitrogen, neutralizes, dehydration after cooling, obtain N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine polyoxy
343.7 parts of ethylene polyethenoxy ether (y=3, z=5), molar yield 84.7%.
(c) preparation of oil base drilling fluid compound emulsifying agent
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 ethoxy propane diamine polyoxyethylene poly-oxygen propylene aether (y=3, z=5) and
10 parts of vegetable oil acid single ethanol amides (are synthesized to obtain, wherein containing with quality percentage by methyl soyate and monoethanolamine
Meter, methyl soyate include following components: tetradecanoic acid formicester 0.557%, palmitinic acid formicester 18.250%, palm
Olefin(e) 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.), the heating stirring at 90 DEG C is uniformly mixed, and obtains the Composite Milk suitable for oil base drilling fluid
Agent.
(d) preparation of full oil base drilling fluid
Weigh 9 grams of the oil base drilling fluid compound emulsifying agent that step (c) obtains, measurement 200mL5# white oil enters stainless steel height
It stirs in cup, high-speed stirred 20min, sequentially adds 6 grams modified of humic acid of cetylamine, butadiene rubber (number-average molecular weight 250,000)
8 grams and 3 grams of CaO powder, continues high-speed stirred 20min, obtain stable full oil base drilling fluid system.It is surveyed with [embodiment 1] (d)
Determine the performance of system, the results are shown in Table 1.
[embodiment 4]
(a) synthesis (x=3) of N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine
55.3 parts of N- ethoxy propane diamine, 8.33 parts of KOH are added to cold equipped with sealing machine stirring, thermometer, straight type
It is solidifying to manage, in the reactor of receiving flask, after 150 DEG C are stirred 1 hour, methyl soyate is slowly added dropwise (with quality percentage
Content meter, methyl soyate include following components: tetradecanoic acid formicester 0.557%, palmitinic acid formicester 18.250%, palm fibre
Palmitic acid olefin(e) acid formicester 1.402%, stearic acid methyl ester 5.495%, oleic acid formicester 30.203%, linoleic acid formicester 36.000%, flax
Sour formicester 3.587%, surplus other.) 277.6 parts, it is added dropwise in 1 hour.It reacts 8 hours at 165 DEG C, is generated in reaction
Methanol be collected into receiving flask by condenser west tube.Remaining low boiling point product and reaction raw materials are evaporated under reduced pressure out,
Obtain target product N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine.
(b) synthesis of N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine polyoxyethylene ether (y=3, z=0)
The N that step (a) is synthesized, N ' -256 parts, 15.4 parts calcium oxide of bis- vegetable oil acids acyl group ethoxy propane diamine and hydrogen
Aoxidizing calcium compound, (calcium oxide and calcium hydroxide weight ratio are added for 1:1) equipped with condensing unit, agitating device and gas dispersion
In the high-pressure reactor of device, when being heated to 135 DEG C in logical nitrogen, 20 parts of water is added, are stirred to react 1 hour.After removing moisture,
80 DEG C are cooled to, high activity, highly selective compound is made in the sulfuric acid (20wt%) that catalyst neutralisation theoretical amount is slowly added dropwise
System temperature is heated to 90 DEG C, opens vacuum system, take off under a high vacuum by calcium oxide alkoxylating catalyst reaction solution system
It water 2 hours, is then purged 3 times with nitrogen, system reaction temperature is adjusted to 160 DEG C and is slowly passed through 34.9 parts of ethylene oxide, controlled
Pressure≤0.60MPa.After reaction, system is purged with nitrogen, is neutralized after cooling, dehydration, obtains N, N '-bis- vegetable oil acids acyl
250.8 parts of base ethoxy propane diamine polyoxyethylene ether (y=3, z=0), molar yield 86.2%.
(c) preparation of oil base drilling fluid compound emulsifying agent
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 full oil base drilling fluid
Weigh 6 grams of the oil base drilling fluid compound emulsifying agent that step (c) obtains, measurement 200mL5# white oil enters stainless steel height
It stirs in cup, high-speed stirred 20min, sequentially adds 3 grams modified of humic acid of cetylamine, butadiene rubber (number-average molecular weight 200,000)
6 grams and 3 grams of CaO powder, continues high-speed stirred 20min, obtain stable anhydrous non-clay full oil base drilling fluid drilling fluid system.
With the performance before and after [embodiment 1] (d) measurement system aging, the results are shown in Table 1.
[comparative example 1]
With (d) in [embodiment 3], difference is with 9g vegetable oil acid single ethanol amide alternative composite emulsifier, remaining phase
Together, the performance of full oil base drilling fluid system is determined, the results are shown in Table 2.
[comparative example 2]
With (d) in [embodiment 3], difference is with N, N '-bis- vegetable oil acids acyl group propane diamine (x=3, y=0, z=0)
It is 3:1 with vegetable oil acid single ethanol amide quality proportioning is that emulsifier dosage 9g substitutes compound emulsifying agent of the invention, remaining phase
Together, the performance of full oil base drilling fluid system is determined.The results are shown in Table 2.
[comparative example 3]
With [embodiment 3] (d), difference is with N, N '-bis- vegetable oil acids acyl group propane diamine polyethenoxy ether (x=3, y
=0, z=3) it with vegetable oil acid single ethanol amide quality proportioning be 3:1 is that emulsifier dosage 9g substitutes composite emulsifying of the invention
Agent, remaining is identical, determines rheological parameter, emulsion-breaking voltage and the API filtration of full oil base drilling fluid system, as a result such as 2 institute of table
Show.
[comparative example 4]
With [embodiment 3] (d), the difference is that the water of different quality is added, remaining is identical, determines full oil base drilling well
The performance of liquid system water resistant infringement, the results are shown in Table 3.
[comparative example 5]
With [embodiment 3] (d), the difference is that the sodium chloride brine of 10g various concentration is added, remaining is identical, measurement
The performance of full oil base drilling fluid system salt resistance water enchroachment (invasion) evil, the results are shown in Table 4.
[comparative example 6]
With [comparative example 5], the difference is that putting it into roller furnace high temperature aging 12h, remaining is identical, determines complete
Performance after oil base drilling fluid system high-temperature aging, the results are shown in Table 5.
The full oil base drilling fluid system performance of table 1
The full oil base drilling fluid system performance of table 2
The full oil base drilling fluid system water resistant of table 3 invades performance
The complete aqueous energy of oil base drilling fluid system salt resistance of table 4
The full oil base drilling fluid system heat-resisting property of table 5
Claims (10)
1. a kind of full oil base drilling fluid includes following components based on mass fraction:
(1) 100 part of base oil；
It (2) include that the compound emulsifying agent of primary emulsion and coemulsifier is no less than 0.5 part, with contained primary emulsion and auxiliary cream
The quality meter of agent；
(3) 0.1~5 parts of tackifier；
(4) 0.5~5 parts of fluid loss additive；
(5) 0~5 parts of alkaline matter；
Wherein, the primary emulsion is selected from least one of structure shown in logical formula (I), and coemulsifier is selected from general formula (II) institute
Show at least one of structure；In mass, the ratio of the primary emulsion and coemulsifier meets 0 < coemulsifier:
Primary emulsion≤1；
R described in logical formula (I)2For hydrogen or R3CO, R1And R3For C11~C23Saturation or unsaturated alkyl or C11~C23's
The mixing alkyl of saturated hydrocarbyl and unsaturated alkyl, x=1~10, y=1~40, z=0~40；R4For C7~C25Aliphatic group,
R5And R6It is independently chosen from H, C2~C4One of hydroxyalkyl.
2. full oil base drilling fluid according to claim 1, it is characterised in that the base oil is diesel oil, white oil, synthetic oil
At least one of.
3. full oil base drilling fluid according to claim 1, it is characterised in that the x=2~6, y=1~20, z=0~
30。
4. full oil base drilling fluid according to claim 1, it is characterised in that the alkaline matter be alkali carbonate,
At least one of alkali metal oxide, calcium oxide or calcium hydroxide.
5. full oil base drilling fluid according to claim 1, it is characterised in that the tackifier are butadiene rubber, butylbenzene rubber
At least one of glue, EP rubbers, polyalkyl methacrylate, bitumen or oxidized asphalt.
6. full oil base drilling fluid according to claim 1, it is characterised in that the fluid loss additive is that long-chain organic amine changes
At least one of property humic acid, bitumen, oxidized asphalt.
7. full oil base drilling fluid according to claim 1, it is characterised in that the anhydrous non-clay oil base drilling fluid
Preparation method the following steps are included:
(a)R1CONH(CH2)xNR2CH2CH2The preparation of OH (i.e. fatty acyl hydroxyethyl diamines):
R in the presence of basic catalyst1COOCH3(i.e. fatty acid methyl ester) and NH2(CH2)xNHCH2CH2OH (i.e. hydroxyethyl diamine)
80~220 DEG C at a temperature of react 2~24 hours, 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)zThe preparation of H (i.e. fatty acyl group diamines Polyoxyalkylene ethers):
In the presence of basic catalyst, fatty acyl hydroxyethyl diamines synthesized by step (a) and required ethylene oxide or ring
Ethylene Oxide is 85~180 DEG C in reaction temperature, and pressure is reacted to obtain the fatty acyl under the conditions of being less than 0.80MPa gauge pressure
Base diamines Polyoxyalkylene ethers；
(c) preparation of compound emulsifying agent:
By the fatty acyl hydroxyethyl diamines that step (a) obtains and/or the fatty acyl group diamines that step (b) obtains
Polyoxyalkylene ethers and the coemulsifier are uniformly mixed in the ratio, obtain the oil base drilling fluid compound emulsifying agent；
(d) preparation of full oil base drilling fluid
The compound emulsifying agent that step (c) obtains is uniformly mixed with base oil, the alkaline matter, tackifier, fluid loss additive,
Obtain the full oil base drilling fluid.
8. full oil base drilling fluid according to claim 7, it is characterised in that in the step (a), subtract after reaction
Unreacted raw material is distilled off for pressure and the methanol of generation obtains the fatty acyl hydroxyethyl diamines.
9. the preparation method of full oil base drilling fluid according to claim 7, it is characterised in that the alkali in the step (a)
Property catalyst be alkali metal hydroxide.
10. the preparation method of full oil base drilling fluid according to claim 7, it is characterised in that in the step (b)
Basic catalyst is at least one of alkaline earth metal hydroxide, alkaline earth oxide.
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