CN105713588B - Non-clay full oil base drilling fluid and preparation method thereof for water-sensitive formation - Google Patents
Non-clay full oil base drilling fluid and preparation method thereof for water-sensitive formation Download PDFInfo
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Abstract
The non-clay full oil base drilling fluid and preparation method thereof that the present invention relates to a kind of for water-sensitive formation, 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 part of base oil；(2) it is no less than 0.5 part of the compound emulsifying agent including primary emulsion and coemulsifier shown in formula (I)；(3) 0.1~5 parts of tackifier；(4) 0.5~5 parts of fluid loss additive；The non-clay 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 non-clay full oil base drilling fluid and preparation method thereof, be suitable for unconventional low pressure and low permeability,
Water sensitivity and water phase activity difference are big and easily cause 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 non-clay full oil base drilling fluid is not aqueous, emulsifier
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 and has
Outside the advantages of water in oil emulsion drilling fluid, above-mentioned deficiency is also overcomed.It is living to can be used for easily collapse stratum, saline bed, especially water phase
Spend the low-pressure stratum and ocean deepwater drilling on the stratum and energy decline that differ 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 non-clay full oil base drilling fluid system of hair, of the present invention is exactly in this case, to be suitable for the non-clay of such stratum
Full oil base drilling fluid.
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 the non-clay full oil base drilling fluid of one kind, meet such oil-gas stratigraphic deposits conventional drilling, big displacement
The special requirements such as exceptional well, seaborne horizontal well.The second technical problem to be solved by the present invention is to provide a kind of and solution technology
The preparation method of the corresponding non-clay full oil base drilling fluid of one of problem.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of non-clay full oil base brill
Well liquid, including 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 formula (II)
At least one of shown structural fatty acid or carboxylate；In mass, the ratio of the primary emulsion and coemulsifier is full
0 < coemulsifier of foot: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, M are selected from H, zinc, iron, aluminium, alkali gold
One of category, alkaline-earth metal, when M is H or alkali metal, n=1, when M is alkaline-earth metal, n=0.5, when M is iron or aluminium
When, n=1/3.
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；M is preferably one of H, zinc or alkaline-earth metal；Auxiliary cream
Agent can be further preferably from one of oleic acid, stearic acid, palmitinic acid, myristic acid, lauric acid, calcium oleate, calcium stearate
Or two kinds or more of mixture；In mass, the ratio of the primary emulsion and coemulsifier is preferably coemulsifier:It is main
Emulsifier=1:(2~20).Base oil is preferably one of white oil, synthetic oil, atoleine or more than one mixture；
Tackifier be preferably one of butadiene rubber, butadiene-styrene rubber, EP rubbers, polyalkyl methacrylate or more than one
Mixture；Fluid loss additive is preferably the modified humic acid of long-chain organic amine, and chain length is preferably C12、C16、C18；Alkaline matter is preferred
For lime powder.
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 non-clay full oil base drilling fluid does not more preferably include well known to those skilled in the art
Oil base drilling fluid usual component organoclay.
In above-mentioned technical proposal, the non-clay full oil base drilling fluid, with contained oil phase and water phase volume total volume meter, more
Preferably include the water of 0-10%.
In above-mentioned technical proposal, the primary emulsion can be further preferably from two or more in structure shown in (I)
Mixture can play preferable synergistic effect.
In above-mentioned technical proposal, the coemulsifier can be further preferably from two or more in structure shown in (II)
Mixture, preferable synergistic effect can be played.
To solve above-mentioned technical problem two, the technical solution adopted in the present invention is as follows：
A kind of preparation method of non-clay full oil base drilling fluid, includes the following steps：
(a)R1CONH(CH2)xNR2CH2CH2The preparation of OH (i.e. fatty acyl hydroxyethyl diamines)
R in the presence of basic catalyst1COOCH3(i.e. fatty acid methyl ester) and NH2(CH2)xNHCH2CH2OH (i.e. 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) by the fatty acyl hydroxyethyl diamines that step (a) obtains and/or the fat that step (b) obtains
Acyl group diamines Polyoxyalkylene ethers and the coemulsifier, it is uniformly mixed by the ratio, the oil base drilling fluid is obtained with compound
Emulsifier；
(d) preparation of non-clay 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 non-clay 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.
Non-clay full oil base drilling fluid prepared by the present invention, due to the emulsifier fatty acyl group diamines Polyoxyalkylene ethers point used
Contain polyoxyethylene, polyoxypropylene non-ionic group and amide group in minor structure simultaneously, makes it have good heat-resistant salt-resistant
Performance so that the oil base drilling fluid have excellent high temperature and high salt under the conditions of stability, water resistant with higher invade and
The ability of salt contamination due to system without emulsification water droplet, without organoclay, therefore will not cause water lock and solid phase pollution to stratum, from
And solve 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 strata drilling mistake
Damage problem in journey to stratum is suitable for the exploration and development and popularization and application of such oil reservoir.
Using the non-clay full oil base drilling fluid prepared by the present invention suitable for water-sensitive formation, 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
Changing calcium compound, (calcium oxide and calcium hydroxide weight ratio are 1:1) N, N '-stearic bicine diester base are reacted to obtain under the action of in 150 DEG C
348.5 parts of dihydroxy ethyl ethylenediamine polyethenoxy ether (y=1, z=10), molar yield 87.7%.
(c) preparation 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 lauric acid and 10 parts of stearic acid, the heating stirring at 85 DEG C are uniformly mixed, and obtain oil base brill
Well liquid compound emulsifying agent.
(d) preparation of non-clay 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 non-clay full oil base drilling fluid system.According to《GB/T 16782-1997 oil base drilling fluid on-the-spot test
Program》Rheological parameter, emulsion-breaking voltage and the API filtration of the drilling fluid system are measured respectively.Wherein rheological parameter uses Qingdao
The fast rotational viscometer of the ZNN-D6 type six of the sensible special instrument factory in sea measures at 50 DEG C, and is counted according to formula (1), (2) and (3)
Calculate plastic viscosity (PV), yield value (YP) and ratio of dynamic shear force/yield value to plastic viscosity (YP/PV)；Emulsion-breaking voltage (ES) is 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) calculates filter loss (FL).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 1 to calcium compound:1) it is added equipped with condensing unit, agitating device and gas distributor
In high-pressure reactor, when being heated to 135 DEG C in logical nitrogen, 20 parts of water is added, are stirred to react 1 hour.After removing moisture, cooling
To 80 DEG C, high activity, highly selective compound oxidizing is made in the sulfuric acid (20wt%) that catalyst neutralisation theoretical amount is slowly added dropwise
System temperature is heated to 80 DEG C, opens vacuum system, be dehydrated 2 under a high vacuum by calcium alkoxylating catalyst reaction solution system
Hour, it is then purged 3 times with nitrogen, system reaction temperature is adjusted to 180 DEG C and is slowly passed through 167.1 parts of ethylene oxide, control pressure
Power≤0.60MPa.After reacting ethylene oxide is complete, 489.4 parts of propylene oxide are added, the reaction was continued in 180 DEG C, and reaction terminates
Afterwards, system is purged with nitrogen, is neutralized after cooling, dehydration, obtain N, N '-bis- erucic acid acyl group ethoxy propane diamine polyoxyethylene is poly-
845.7 parts of oxypropylene ether (y=10, z=20), molar yield 85.6%.
(c) preparation 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 calcium oleates, the heating stirring at 85 DEG C are uniformly mixed, obtain oil base drilling fluid
Use compound emulsifying agent.
(d) preparation of 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 non-clay full oil base drilling fluid system.Together【Implement
Example 1】(d) performance of system is measured, 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 1:1) it is added equipped with condensing unit, agitating device and gas dispersion
In the high-pressure reactor of device, when being heated to 135 DEG C in logical nitrogen, 20 parts of water is added, are stirred to react 1 hour.After removing moisture,
80 DEG C are cooled to, high activity, highly selective compound is made in the sulfuric acid (20wt%) that catalyst neutralisation theoretical amount is slowly added dropwise
System temperature is heated to 90 DEG C, opens vacuum system, take off under a high vacuum by calcium oxide alkoxylating catalyst reaction solution system
It water 2 hours, is then purged 3 times with nitrogen, system reaction temperature is adjusted to 160 DEG C and is slowly passed through 34.9 parts of ethylene oxide, controlled
Pressure≤0.60MPa.After reacting ethylene oxide is complete, 114.8 parts of propylene oxide are added, the reaction was continued in 160 DEG C, reaction knot
Shu Hou purges system with nitrogen, neutralizes, dehydration after cooling, obtain N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine polyoxy
343.7 parts of vinethene (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 oleic acid, the heating stirring at 90 DEG C are uniformly mixed, obtain oil base drilling fluid compound emulsifying agent.
(d) preparation of non-clay 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 non-clay full oil base drilling fluid system.Together【Embodiment
1】(d) performance of system is measured, 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 1:1) it is added equipped with condensing unit, agitating device and gas dispersion
In the high-pressure reactor of device, when being heated to 135 DEG C in logical nitrogen, 20 parts of water is added, are stirred to react 1 hour.After removing moisture,
80 DEG C are cooled to, high activity, highly selective compound is made in the sulfuric acid (20wt%) that catalyst neutralisation theoretical amount is slowly added dropwise
System temperature is heated to 90 DEG C, opens vacuum system, take off under a high vacuum by calcium oxide alkoxylating catalyst reaction solution system
It water 2 hours, is then purged 3 times with nitrogen, system reaction temperature is adjusted to 160 DEG C and is slowly passed through 34.9 parts of ethylene oxide, controlled
Pressure≤0.60MPa.After reaction, system is purged with nitrogen, is neutralized after cooling, dehydration, obtains N, N '-bis- vegetable oil acids acyl
250.8 parts of base ethoxy propane diamine polyoxyethylene ether (y=3, z=0), molar yield 86.2%.
(c) preparation of oil base drilling fluid compound emulsifying agent
In terms of mass fraction, the N that 150 parts of steps (b) are obtained, N '-bis- vegetable oil acids acyl group ethoxy propane diamine polyoxy
Vinethene (y=3, z=0) and 50 parts of calcium stearates, the heating stirring at 80 DEG C are uniformly mixed, and are obtained for oil base drilling fluid
Compound emulsifying agent.
(d) preparation of non-clay 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 non-clay full oil base drilling fluid drilling fluid system.Together
【Embodiment 1】(d) performance before and after system aging is measured, the results are shown in Table 1.
【Comparative example 1】
Together【Embodiment 3】In (d), for difference with 9g oleic acid alternative composite emulsifier, remaining is identical, determines non-clay
The performance of full oil base drilling fluid system, the results are shown in Table 2.
【Comparative example 2】
Together【Embodiment 3】In (d), difference is with N, N '-bis- vegetable oil acids acyl group propane diamine (x=3, y=0, z=0)
It is 4 with oleic acid quality proportioning:1 substitutes compound emulsifying agent of the invention for emulsifier 9g, remaining is identical, determines non-clay full oil
The performance of base drilling fluid system.The results are shown in Table 2.
【Comparative example 3】
Together【Embodiment 3】(d), difference is with N, N '-bis- vegetable oil acids acyl group propane diamine polyethenoxy ether (x=3, y
=0, z=3) with oleic acid quality proportioning be 4:1 substitutes compound emulsifying agent of the invention for emulsifier 9g, remaining is identical, determines
Rheological parameter, emulsion-breaking voltage and the API filtration of non-clay full oil base drilling fluid system, the results are shown in Table 2.
【Comparative example 4】
Together【Embodiment 3】(d), the difference is that the water of different quality is added, remaining is identical, determines non-clay full oil
The performance of base drilling fluid system water resistant infringement, the results are shown in Table 3.
【Comparative example 5】
Together【Embodiment 3】(d), the difference is that the sodium chloride brine of 10g various concentration is added, remaining is identical, measurement
The performance of non-clay full oil base drilling fluid system salt resistance water enchroachment (invasion) evil, the results are shown in Table 4.
【Comparative example 6】
Together【Comparative example 5】, the difference is that putting it into roller furnace high temperature aging 12h, remaining is identical, determines nothing
Performance after the full oil base drilling fluid system high-temperature aging of clay, the results are shown in Table 5.
Table 1 is used for the non-clay full oil base drilling fluid system performance of water-sensitive formation
Table 2 is used for the non-clay full oil base drilling fluid system performance of water-sensitive formation
Non-clay full oil base drilling fluid system water resistant of the table 3 for water-sensitive formation invades performance
Table 4 is used for the non-clay complete aqueous energy of oil base drilling fluid system salt resistance of water-sensitive formation
Table 5 is used for the non-clay full oil base drilling fluid system heat-resisting property of water-sensitive formation
Claims (11)
1. a kind of non-clay full oil base drilling fluid, including following components：
The base oil of (1) 100 parts by volume；
It (2) include that the compound emulsifying agent of primary emulsion and coemulsifier is no less than 0.5 mass parts, with contained primary emulsion and auxiliary
The quality meter of assistant for emulsifying agent；
The tackifier of (3) 0.1~5 mass parts；
The fluid loss additive of (4) 0.5~5 mass parts；
The alkaline matter of (5) 0~5 mass parts；
Wherein, mass parts/parts by volume is g/mL；
Wherein, the primary emulsion is selected from least one of structure shown in logical formula (I), and coemulsifier is selected from shown in formula (II)
At least one of structural fatty acid or carboxylate；In mass, the ratio of the primary emulsion and coemulsifier meets 0 <
Coemulsifier:Primary emulsion≤1；
R4-COO(M)n, (II)
In general formula, the R2For hydrogen or R3CO, the R1And R3For C11~C23Saturation or unsaturated alkyl or C11~C23
Saturated hydrocarbyl and unsaturated alkyl mixing alkyl, x=1~10, y=1~40, z=0~40；R4For C7~C25Aliphatic hydrocarbon
Base, M are selected from one of H, zinc, iron, aluminium, alkali metal, alkaline-earth metal, when M is H or alkali metal, n=1, when M is zinc or alkali
When earth metal, n=0.5, when M is iron or aluminium, n=1/3.
2. non-clay full oil base drilling fluid according to claim 1, it is characterised in that the base oil be diesel oil, white oil,
At least one of synthetic oil.
3. non-clay 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. non-clay full oil base drilling fluid according to claim 1, it is characterised in that the alkaline matter is alkali metal
At least one of carbonate, alkali metal oxide, calcium oxide or calcium hydroxide.
5. non-clay full oil base drilling fluid according to claim 1, it is characterised in that the tackifier be butadiene rubber,
At least one of butadiene-styrene rubber, EP rubbers, polyalkyl methacrylate, bitumen or oxidized asphalt.
6. non-clay full oil base drilling fluid according to claim 1, it is characterised in that the fluid loss additive has for long-chain
At least one of machine amine modified humic acid, bitumen, oxidized asphalt.
7. non-clay full oil base drilling fluid according to claim 1, it is characterised in that the non-clay oil base drilling fluid
Preparation method include the following steps：
(a)R1CONH(CH2)xNR2CH2CH2The preparation of OH (i.e. fatty acyl hydroxyethyl diamines)：
R in the presence of basic catalyst1COOCH3(i.e. fatty acid methyl ester) and NH2(CH2)xNHCH2CH2OH (i.e. 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 non-clay 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, is obtained
To the non-clay full oil base drilling fluid.
8. the preparation method of non-clay full oil base drilling fluid according to claim 1, it is characterised in that include the following steps：
(a)R1CONH(CH2)xNR2CH2CH2The preparation of OH (i.e. fatty acyl hydroxyethyl diamines)：
R in the presence of basic catalyst1COOCH3(i.e. fatty acid methyl ester) and NH2(CH2)xNHCH2CH2OH (i.e. 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 non-clay 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, is obtained
To the non-clay full oil base drilling fluid.
9. the preparation method of non-clay full oil base drilling fluid according to claim 8, it is characterised in that the step (a)
In basic catalyst be alkali metal hydroxide.
10. the preparation method of non-clay full oil base drilling fluid according to claim 8, it is characterised in that the step
(b) basic catalyst in is at least one of alkaline earth metal hydroxide, alkaline earth oxide.
11. non-clay full oil base drilling fluid according to claim 8, it is characterised in that：
Vacuum distillation after reaction in the step (a) removes unreacted raw material and the methanol of generation obtains the fat
Acyl group hydroxyethyl diamine.
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