CN104232030B - Oil base drilling fluid emulsifying agent and preparation method thereof - Google Patents
Oil base drilling fluid emulsifying agent and preparation method thereof Download PDFInfo
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- CN104232030B CN104232030B CN201310237577.XA CN201310237577A CN104232030B CN 104232030 B CN104232030 B CN 104232030B CN 201310237577 A CN201310237577 A CN 201310237577A CN 104232030 B CN104232030 B CN 104232030B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
- C09K8/36—Water-in-oil emulsions
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2633—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen the other compounds containing amide groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
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- C08G65/2651—Alkaline earth metals or compounds thereof
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- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics
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Abstract
The present invention relates to a kind of oil base drilling fluid emulsifying agent and preparation method thereof, oil base drilling fluid emulsifying agent less varieties in the prior art, the problem of emulsifiability, heat resistance are poor are mainly solved.The present invention is by using one kind such as formula(Ⅰ)The technical scheme of shown oil base drilling fluid emulsifying agent and preparation method thereof, preferably resolve above mentioned problem, it can be used as oil base drilling fluid emulsifying agent, with good emulsifiability and heat resistance, the oil base drilling fluid stability of formation, temperature tolerance are preferable, meet in the drillng operations of occasion such as strong retraction in oil field, high-temperature stratum drilling well and big displacement Special Drilling Operation, seaborne horizontal well.
Description
Technical field
The present invention relates to a kind of oil base drilling fluid emulsifying agent and preparation method thereof.
Background technology
Continuous reduction and exploitation difficulty with petroleum reserves, countries in the world are increased to deep formation petroleum resources one after another
The input of exploration and development, develops an urgent demand that new oil reservoir has become current each major oil companies' development.China waits to verify
Petroleum resources be mainly distributed on Tarim Basin, Zhunger Basin, Qaidam, tell the basins such as Kazakhstan, Sichuan, the 73% of its stock number is imbedded in
Deep layer, and underground condition complex, therefore deep-well and ultradeep well oil gas drilling and supporting development technique have turned into restriction oil
The key factor of gas development of resources.With the increase of depth of stratum, deep-well, ultradeep well formation temperature also can more and more higher, ground
Can the hot environment of layer maintain stable performance to bring great challenge to drilling fluid.
Drilling fluid is as the important component of drilling engineering, and its performance is directly connected to the drilling well matter of deep-well, ultradeep well
Amount, drilling cost and drilling period.Relative to water-base drilling fluid, oil base drilling fluid has stronger anti-collapse inhibition, lubricity
With good reservoir protection performance, strong retraction and high temperature, superhigh temperature stratum can be especially met, or needs to bore big displacement exceptional well
And seaborne horizontal well etc. is special turns drilling well needs.Oil base drilling fluid, also known as Water-In-Oil drilling fluid, are by oil, water, emulsifying agent, drop
Fluid loss agents, equilibrium of activation agent, flow pattern regulator etc. are constituted.Usually used Water-In-Oil drilling fluid water content is between 5~30 %
(generally referred to as full oil base drilling fluid of the water content within 5%, not referred to as Water-In-Oil drilling fluid), but high temperature resistance up to 180 DEG C with
On Water-In-Oil drilling fluid reclaimed water content it is general in 5~10 %, rarely exceed 15%.The content increase of water, takes bits property, drop filter
The property lost and suspension, rheological characteristic all improve, but heat endurance and electrical stability are all deteriorated, and such as CN1660958 reports a kind of conjunction
Into base drilling fluid, the primary emulsion used is the mixture of AESA and NPE,
Although still having good rheological characteristic and emulsion-breaking voltage after 16 hours in 150 DEG C of agings, water content is up to 25%.Patent CN
A kind of high-temperature water-in-oil drilling fluid of 102031095 A Shen Qing Publications, although heatproof can be to 240 DEG C, but it must be by auxiliary breast
The presence of agent and calcium oxide can be only achieved application effect.Oil base drilling fluid is therefore expensive because base fluid is based on oil, into
This height, full oil base drilling fluid is even more so, as CN101215461 reports a kind of complete-oil synthetic base drilling fluid, the emulsification used
Agent is one or more mixtures in Long carbon chain fatty acid amide, Long carbon chain alkyl benzene calcium sulfonate, polyolefin carboxylic acid ester, to the greatest extent
Pipe has the advantages that low toxicity, environmental protection, small to reservoir damage, but it prepares cost height, limits it and promotes the use of.
There is provided of less types as oil base drilling fluid emulsifying agent in the market, and report the breast for intensified oil reduction
Agent kind is relatively more, and such as US4485873, US4545912, CN100531884 report polyoxyethylated alkyl phenol second
Hydrochlorate, double tail chain polyoxyethylene sulfonic acid salt, alkyl-fragrant benzyl-polyethenoxy ether anion surfactant answering in terms of intensified oil reduction
With, but it is not directed to its purposes in terms of well-drilling liquid emulgent.It is in terms of domestic oil base drilling fluid emulsifying agent to rely on external more
Product, and domestic supporting drilling fluid system is also less.
Oil base drilling fluid due to limited by cost, environmental requirement develop always it is relatively slow, the block of application also compared with
Few, as existing oilfield reserve increasingly declines, and the exploitation in new exploratory area can run into various bad grounds and environment, be badly in need of carrying out
Satisfaction prepares the research of stability and high efficiency oil base drilling fluid emulsifying agent, to solve oil base drilling fluid emulsifying agent less varieties, emulsibility
Can be poor, not the problem of salt tolerant, non-heatproof, the cost of reduction oil base drilling fluid is reached by improving the ratio of oil base drilling fluid reclaimed water
Problem, to provide technical support extensively using oil base drilling fluid operation.
In the case of exactly this high-moisture of the present invention, it is suitable for preparing the breast of stability and high efficiency oil base drilling fluid
Agent and preparation method thereof.
The content of the invention
One of technical problems to be solved by the invention are oil base drilling fluid emulsifying agent less varieties, emulsibility in the prior art
There is provided a kind of oil base drilling fluid emulsifying agent for the problem of energy, heat resistance are poor.Oil base drilling fluid emulsifying agent has good
Emulsifiability and heat resistance, the oil base drilling fluid containing such oil base drilling fluid emulsifying agent can meet strong retraction in oil field, height
The special requirement such as warm stratum and big displacement Special Drilling Operation, seaborne horizontal well drilling well.The two of the technical problems to be solved by the invention
It is to provide a kind of preparation method with solving one of technical problem corresponding oil base drilling fluid emulsifying agent.
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 oil base drilling fluid emulsifying agent, its molecular formula is:
,(I)
Wherein R1For containing C8~C30Saturation or unsaturated alkyl, R2For hydrogen or R3CO, R3For C8~C30Saturation or unsaturation
Alkyl, x=1~10, y=1~40, z=0~40.
In above-mentioned technical proposal, described R1And R3It is independently selected from C11~C23Saturation or undersaturated alkyl or C11~
C23Saturated hydrocarbyl and unsaturated alkyl mixing alkyl.More preferably R1And R3It is 11,13, ten to be independently selected from carbon number
5th, 17,19,21 saturated hydrocarbons or unsaturated alkyl, or 11,13,15,17,19,21 it is full
With hydrocarbon and the mixing alkyl of unsaturated hydrocarbons.It is preferred that it is that 1 ~ 20, z is 0~30 that x, which is 2 ~ 6, y,;Further preferred x be 2 or 3, y be 1 ~
10;More preferably z is 0 ~ 20.
To solve the two of above-mentioned technical problem, the technical solution adopted in the present invention is as follows:
A kind of preparation method of oil base drilling fluid emulsifying agent, comprises the following steps:
(a) R1CONH(CH2)xNR2CH2CH2OH(That is fatty acyl hydroxyethyl diamines)Preparation
The R in the presence of base catalyst1COOCH3(That is fatty acid methyl ester)With NH2(CH2)xNHCH2CH2OH(That is ethoxy
Diamines)Reacted 2~24 hours at a temperature of 80 ~ 220 DEG C, reaction terminate after preferably vacuum distillation remove unreacted raw material and
The methanol of generation obtains the fatty acyl hydroxyethyl diamines.Wherein, the mol ratio of fatty acid methyl ester and hydroxyethyl diamine is excellent
Select 1: 0.1~6.The catalyst amount preferably accounts for the 0.01 ~ 10% of fatty acid methyl ester quality.
(b) R1CONH(CH2)xNR2(CH2CH2O)y-(CH2CHCH3O)zH(That is fatty acyl group diamines Polyoxyalkylene ethers)System
It is standby:
In the presence of base catalyst, step(a)Synthesized fatty acyl hydroxyethyl diamines and required oxirane
Or expoxy propane react and obtains described fat acyl group diamines Polyoxyalkylene ethers.Catalyst amount is preferably fatty acyl hydroxyethyl
The 0.5~6.0% of diamines quality.
In above-mentioned technical proposal, a) the reaction temperature preferred scope in step is 100 ~ 200 DEG C, more preferably 120 ~ 180
℃;Catalyst is preferably at least one of alkali metal hydroxide, alkaline earth metal hydroxide, more preferably potassium hydroxide,
Sodium hydroxide, more preferably potassium hydroxide, consumption are preferably account for fatty acid methyl esters monomer mass 0.5~5.0%;Fat
The mol ratio of fatty acid methyl esters and hydroxyethyl diamine is preferably 1 ~ 2: 1;Reaction time is preferably 6 ~ 16 hours.
b)Base catalyst in step is preferably at least one in alkaline earth oxide, alkaline earth metal hydroxide
Plant, more preferably at least one of calcium oxide, calcium hydroxide, catalyst amount is preferably to account for fatty acyl hydroxyethyl diamines matter
The 1~5.0% of amount.Reaction temperature is preferably 85~180 DEG C, and pressure is preferably smaller than 0.80MPa gauge pressures.
The oil base drilling fluid emulsifying agent of fatty acyl group diamines Polyoxyalkylene ethers prepared by the present invention has good heatproof
And salt resistant character, and with good dissolubility and emulsion stability, and the oil base drilling fluid emulsifying agent have it is nontoxic, harmless,
The good advantage of biological degradability, is suitable for the oil base drilling fluid emulsifying agent as high temperature and high salt water-sensitive strata;In addition originally
The preparation method of invention is simple and easy to apply, and raw material is easy to get, with preferable economic feasibility, suitable industrial application.
The fatty acyl group diamines Polyoxyalkylene ethers class surfactant prepared using the present invention can be used alone as oil base drilling fluid
Emulsifying agent, the characteristics of with good emulsion stability, achieve preferable technique effect.Oil base for example including following component is bored
Well liquid heatproof, more than emulsion-breaking voltage >=1000V after 180 DEG C, API filtration≤1ml, high temperature ageing, is that a kind of heat resistance is excellent
Good, filter loss is small, good emulsion stability oil base drilling fluid system:60 ~ 90 parts of base oil, 10 ~ 40 parts of water, emulsifying agent 0.5 ~ 5
Part, 1 ~ 5 part of organoclay, 0.5 ~ 3 part of tackifier, 0.5 ~ 3 part of fluid loss additive, 0 ~ 3 part of alkaline matter.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
(a)The synthesis of N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine(x=3)
55.3 parts of N- ethoxys propane diamine, 8.33 parts of KOH are added to cold equipped with sealing machine stirring, thermometer, straight type
In solidifying pipe, the reactor of receiving flask, after 150 DEG C are stirred 1 hour, 277.6 parts of methyl soyate is slowly added dropwise, 1 is small
When interior completion of dropping.Reacted 8 hours at 165 DEG C, the methanol generated in reaction is collected into receiving flask by condenser west tube
In.Vacuum distillation goes out remaining low boiling product and reaction raw materials, obtains target product N, N '-bis- vegetable oil acids acyl group hydroxyl
Ethyl propane diamine.
(b)N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine polyoxyethylene poly-oxygen propylene aether(Y=3, z=5)Synthesis
By step(a)The N of synthesis, N ' -256 parts, 15.4 parts calcium oxide of bis- vegetable oil acids acyl group ethoxy propane diamine and hydrogen
Aoxidize calcium compound(Calcium oxide and calcium hydroxide weight ratio are 1:1)Add scattered equipped with condensing unit, agitating device and gas
In the high-pressure reactor of device, when being heated to 135 DEG C in logical nitrogen, 20 parts of water, stirring reaction 1 hour are added.Remove after moisture,
80 DEG C are cooled to, the sulfuric acid of catalyst neutralisation theoretical amount is slowly added dropwise(20wt%)Be made high activity, high selectivity it is compound
Calcium oxide alkoxylating catalyst reaction solution system, 90 DEG C are heated to by system temperature, are opened vacuum system, are taken off under a high vacuum
Water 2 hours, is then purged 3 times with nitrogen, system reaction temperature is adjusted into 160 DEG C and is slowly passed through 34.9 parts of oxirane, is controlled
Pressure≤0.60MPa.After reacting ethylene oxide is complete, 114.8 parts of expoxy propane are added, continue to react in 160 DEG C, reaction knot
Shu Hou, system is purged with nitrogen, is neutralized, is dehydrated after cooling, obtains N, N '-bis- vegetable oil acids acyl group AEEA polyoxy
Vinethene(Y=3, z=5)343.7 parts, molar yield 84.7%.
【Embodiment 2】
(a)The preparation of N, N '-bis- erucic acid acyl group ethoxy propane diamine(x=3)
47.13 parts, KOH5.6 parts of N- ethoxys propane diamine is added to cold equipped with sealing machine stirring, thermometer, straight type
In solidifying pipe, the reactor of receiving flask, it is added dropwise in after 150 DEG C of stirrings 1 hour, being slowly added dropwise in 281.3 parts, 1 hour of methyl erucate
Finish.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.Vacuum distillation goes out remaining low boiling product and reaction raw materials, obtains target product N, N '-bis- erucic acid acyl group ethoxy
Propane diamine.
(b)N, N '-bis- erucic acid acyl group ethoxy propane diamine polyoxyethylene poly-oxygen propylene aether(Y=10, z=20)Synthesis
By step(a)The N of synthesis, N ' -320 parts, 9.6 parts calcium oxide of bis- erucic acid acyl group ethoxy propane diamine and hydroxide
Calcium compound(Calcium oxide and calcium hydroxide weight ratio are 1:1)Add 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, stirring reaction 1 hour are added.Remove after moisture, cooling
To 80 DEG C, the sulfuric acid of catalyst neutralisation theoretical amount is slowly added dropwise(20wt%)High activity, the compound oxidizing of high selectivity is made
Calcium alkoxylating catalyst reaction solution system, 80 DEG C are heated to by system temperature, open vacuum system, 2 are dehydrated under a high vacuum
Hour, then purged 3 times with nitrogen, system reaction temperature is adjusted into 180 DEG C is slowly passed through 167.1 parts of oxirane, control pressure
Power≤0.60MPa.After reacting ethylene oxide is complete, 489.4 parts of expoxy propane are added, continue to react in 180 DEG C, reaction terminates
Afterwards, system is purged with nitrogen, neutralizes, is dehydrated after cooling, obtain N, N '-bis- erucic acid acyl group ethoxy propane diamine polyoxyethylene gathers
Oxypropylene ether(Y=10, z=20)845.7 parts, molar yield 85.6%.
【Embodiment 3】
(a)The synthesis of N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine(x=3)
55.3 parts of N- ethoxys propane diamine, 8.33 parts of KOH are added to cold equipped with sealing machine stirring, thermometer, straight type
In solidifying pipe, the reactor of receiving flask, after 150 DEG C are stirred 1 hour, 277.6 parts of methyl soyate is slowly added dropwise, 1 is small
When interior completion of dropping.Reacted 8 hours at 165 DEG C, the methanol generated in reaction is collected into receiving flask by condenser west tube
In.Vacuum distillation goes out remaining low boiling product and reaction raw materials, obtains target product N, N '-bis- vegetable oil acids acyl group hydroxyl
Ethyl propane diamine.
(b)N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine APEO(Y=3, z=0)Synthesis
By step(a)The N of synthesis, N ' -256 parts, 15.4 parts calcium oxide of bis- vegetable oil acids acyl group ethoxy propane diamine and hydrogen
Aoxidize calcium compound(Calcium oxide and calcium hydroxide weight ratio are 1:1)Add scattered equipped with condensing unit, agitating device and gas
In the high-pressure reactor of device, when being heated to 135 DEG C in logical nitrogen, 20 parts of water, stirring reaction 1 hour are added.Remove after moisture,
80 DEG C are cooled to, the sulfuric acid of catalyst neutralisation theoretical amount is slowly added dropwise(20wt%)Be made high activity, high selectivity it is compound
Calcium oxide alkoxylating catalyst reaction solution system, 90 DEG C are heated to by system temperature, are opened vacuum system, are taken off under a high vacuum
Water 2 hours, is then purged 3 times with nitrogen, system reaction temperature is adjusted into 160 DEG C and is slowly passed through 34.9 parts of oxirane, is controlled
Pressure≤0.60MPa.After reaction terminates, system is purged with nitrogen, neutralizes, be dehydrated after cooling, obtain N, N '-bis- vegetable oil acids acyl
Base ethoxy propane diamine APEO(Y=3, z=0)250.8 parts, molar yield 86.2%.
【Embodiment 4】
(a)The synthesis of N, N '-stearic bicine diester base AEEA(x=2)
49 parts of N-hydroxyethyl-ethylenediamine, 2.7 parts of KOH are added to equipped with sealing machine stirring, thermometer, the condensation of straight type
Pipe, in the reactor of receiving flask, dripped in after 145 DEG C of stirrings 1 hour, being slowly added dropwise in 270 parts, 1 hour of methyl stearate
Finish.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 product and reaction raw materials are distillated, target product N, N '-stearic bicine diester base AEEA is obtained.
(b)N, N '-stearic bicine diester base AEEA polyethenoxy ether(Y=1, z=10)Synthesis
203 grams of N, N '-stearic bicine diester base AEEA and 185.4 parts of expoxy propane are in 7.6 parts of calcium oxide and hydrogen-oxygen
Change calcium compound(Calcium oxide and calcium hydroxide weight ratio are 1:1)In the presence of N, N '-stearic bicine diester base are reacted to obtain in 150 DEG C
Dihydroxy ethyl ethylenediamine polyethenoxy ether(Y=1, z=10)348.5 parts, molar yield 87.7%.
【Embodiment 5】
a)The preparation of lauroyl AEEA(X=2, y=1, z=0)
By 17 parts of N-hydroxyethyl-ethylenediamine, 1.75 parts of KOH be added to equipped with sealing machine stirring, thermometer, condenser pipe,
In the reactor of receiving flask, in after 120 DEG C of stirrings 1 hour, completion of dropping in 35 parts, 1 hour of methyl laurate is slowly added dropwise.
Reacted 6 hours at 155 DEG C, the condensed pipe of methanol generated in reaction is collected into receiving flask, and then vacuum distillation goes out remaining
Low boiling product and reaction raw materials, obtain 39.7 parts of target product fatty acyl hydroxyethyl ethylenediamine.
【Embodiment 6】
(a)The preparation of lauroyl AEEA(x=2)
17 parts of N-hydroxyethyl-ethylenediamine, 0.35 part of KOH are added to equipped with sealing machine stirring, thermometer, the condensation of straight type
Pipe, in the reactor of receiving flask, dripped in after 150 DEG C of stirrings 1 hour, being slowly added dropwise in 70 parts, 1 hour of methyl laurate
Finish.Reacted 16 hours at 180 DEG C, the methanol generated in reaction is collected into receiving flask by condenser west tube, decompression is steamed
Remaining low boiling product and reaction raw materials are distillated, target product fatty acyl hydroxyethyl ethylenediamine is obtained.
(b)N, N '-bis- lauroyls AEEA APEO(Y=5, z=0)Synthesis
By step(a)The N of synthesis, N ' -70 parts of bis- lauroyls AEEA, 3.5 parts of calcium oxide and calcium hydroxide
Mixture(Calcium oxide and calcium hydroxide weight ratio are 1:1)Add the height equipped with condensing unit, agitating device and gas distributor
Press in reactor, when being heated to 135 DEG C in logical nitrogen, add 20 parts of water, stirring reaction 1 hour.Remove after moisture, be cooled to
80 DEG C, the sulfuric acid of catalyst neutralisation theoretical amount is slowly added dropwise(20wt%)High activity, the compound oxidizing calcium of high selectivity is made
Alkoxylating catalyst reaction solution system, 90 DEG C are heated to by system temperature, open vacuum system, 2 are dehydrated under a high vacuum small
When, then purged 4 times with nitrogen, system reaction temperature is adjusted into 140 DEG C is slowly passed through 26.4 parts of oxirane, control pressure≤
0.60MPa.After reaction terminates, system is purged with nitrogen, neutralizes, be dehydrated after cooling, obtain N, N '-bis- fatty acyl hydroxyethyls second
Diamines APEO(y=5)83 parts, molar yield 86.2%.
【Embodiment 7】
With【Embodiment 1】The N of synthesis, N '-bis- vegetable oil acids acyl group ethoxy propane diamine polyoxyethylene poly-oxygen propylene aether(x
=3, y=3, z=5)For emulsifying agent, oil base drilling fluid system is prepared, the basic recipe used is 210mL5# white oil+90mL 20wt%
CaCl2The wt/vol% organoclays of the wt/vol% of the aqueous solution+3 emulsifying agents+3(The montmorillonite that hexadecyltrimethylammonium chloride is modified)
The butadiene rubber of humic acid+1% that+1 wt/vol% cetylamines are modified(Number-average molecular weight 250,000)+ 1 wt/vol% CaO powders.
Specific experiment process is:210mL5# white oils are taken, 3 wt/vol% emulsifying agents is then added, stirs, then successively
3 wt/vol % organoclays, 1 wt/vol % modified humic acids, 1% butadiene rubber and 1 wt/vol% CaO powders are added, is continued
Stir, be eventually adding 90mL 20wt%CaCl2The aqueous solution, is stirred for uniform, the water-in-oil type wellbore fluid stablized
System.According to《GB/T 16782-1997 oil base drilling fluid On-Site Test Procedures》The water-in-oil type drilling fluid system is determined respectively
Rheological parameter, emulsion-breaking voltage and API filtration.Wherein rheological parameter uses the ZNN-D6 types six of the sensible instrumentation factory in Qingdao sea
Determined under fast 50 degrees Celsius of rotation viscometer, and according to formula(1)、(2)With(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)Surveyed by the DWY-2 type drilling fluids electrical stability of the sensible instrumentation factory in Qingdao
Determine to determine at 50 DEG C of instrument, API filtration is determined by the multi-joint filtration device of SD types, and according to formula(4)Calculate filter loss (FL).
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)
The above-mentioned water-in-oil type drilling fluid prepared is put into XGRL-4 type high temp roller heating furnaces, 180 DEG C of high temperature are old
Change 16h, rheological parameter, emulsion-breaking voltage and the API filtration of the water-in-oil type drilling fluid system, instrument and mistake are determined respectively
Before journey is with aging, as a result as shown in table 1.
【Embodiment 8】
With【Embodiment 2】The N of synthesis, N '-bis- erucic acid acyl group ethoxy propane diamine polyoxyethylene poly-oxygen propylene aether(X=3, y
=10, z=20)For emulsifying agent, oil base drilling fluid system is prepared, the basic recipe used is 195mL atoleines+105mL
20wt%CaCl2The wt/vol% organoclays of the wt/vol% of the aqueous solution+3 emulsifying agents+4(What cetyl trimethylammonium bromide was modified has
Machine soil)The butadiene rubber of humic acid+1% that+1 wt/vol% cetylamines are modified(Number-average molecular weight 180,000)+1.5 wt/vol% CaO
Powder.Together【Embodiment 7】Experimentation, determines rheological parameter before and after the water-in-oil type drilling fluid system aging, demulsification respectively
Voltage and API filtration, test result are as shown in table 1.
【Embodiment 9】
With【Embodiment 3】The N of synthesis, N '-bis- vegetable oil acids acyl group ethoxy propane diamine APEO(X=3, y=3, z
=0)For emulsifying agent, oil base drilling fluid system is prepared, the basic recipe used is 210mL5# white oil+90mL 20wt% CaCl2Water
The wt/vol% organoclays of the wt/vol% of solution+3 emulsifying agents+3(The organoclay that hexadecyltrimethylammonium chloride is modified)+1 wt/
The butadiene rubber of humic acid+1% that vol% cetylamines are modified(Number-average molecular weight 200,000)+ 1 wt/vol% CaO powders.Together【Embodiment
7】Specific experiment process, determines rheological parameter, emulsion-breaking voltage and the API filters before and after the water-in-oil type drilling fluid system aging respectively
Vector, test result is as shown in table 1.
【Embodiment 10】
With【Embodiment 4】The N of synthesis, N '-stearic bicine diester base AEEA polyethenoxy ether(X=2, y=1, z=10)
For emulsifying agent, oil base drilling fluid system is prepared, the basic recipe used is 210mL atoleine+90mL 20wt% CaCl2Water
The wt/vol% organoclays of the wt/vol% of solution+2 emulsifying agents+3.5(The organoclay that cetyl trimethylammonium bromide is modified)+2
The wt/vol % EP rubbers of humic acid+2 that wt/vol% lauryl amines are modified(Number-average molecular weight 50,000)With polymethylacrylic acid 16
Arrcostab(Number-average molecular weight 500,000)The wt/vol% CaO powders of mixture+1.Together【Embodiment 7】Specific experiment process, is surveyed respectively
Rheological parameter, emulsion-breaking voltage and API filtration before and after the fixed water-in-oil type drilling fluid system aging, the test result such as institute of table 1
Show.
【Embodiment 11】
With【Embodiment 5】The preparation of the lauroyl AEEA of synthesis(X=2, y=1, z=0)For emulsifying agent, prepare
Oil base drilling fluid system, the basic recipe used is 270mL5# white oil+30mL 20wt% CaCl2The wt/vol% of the aqueous solution+2 breasts
The wt/vol% organoclays of agent+3(The organoclay that cetyl trimethylammonium bromide is modified)What+1 wt/vol% cetylamines were modified
The wt/vol % EP rubbers of humic acid+1(Number-average molecular weight 150,000)+ 1 wt/vol% CaO powders.Together【Embodiment 7】It is specific real
Process is tested, rheological parameter, emulsion-breaking voltage and API filtration before and after the water-in-oil type drilling fluid system aging are determined respectively, is surveyed
Test result is as shown in table 1.
【Embodiment 12】
With【Embodiment 6】The N of synthesis, N '-bis- lauroyls AEEA APEO(X=2, y=5, z=0)
For emulsifying agent, prepare oil base drilling fluid system, the basic recipe used for the 240mL5# white oil+60mL 25wt%NaCl aqueous solution+
The wt/vol% organoclays of 4 wt/vol% emulsifying agents+2(The organoclay that hexadecyltrimethylammonium chloride is modified)+ 1 wt/vol% ten
The wt/vol % butadiene-styrene rubber of humic acid+1 that hexamine is modified(Number-average molecular weight 200,000)+ 2 wt/vol% CaO powders.Together【Implement
Example 7】Specific experiment process, determines rheological parameter, emulsion-breaking voltage and the API before and after the water-in-oil type drilling fluid system aging respectively
Filter loss, test result is as shown in table 1.
Table 1
【Comparative example 1】
Together【Embodiment 7】, difference is with 3 wt/vol % Arlacel-80s(Span-80)Substitute 3 wt/vol %N, N '-
Double vegetable oil acid acyl group AEEA polyoxyethylene poly-oxygen propylene aethers(X=3, y=3, z=5)For emulsifying agent, remaining is identical, surveys
Rheological parameter, emulsion-breaking voltage and the API filtration of water-in-oil type drilling fluid system are determined, as a result as shown in table 2.Contrast table 1 is counted
It is relatively low according to the system yield value, the emulsion-breaking voltage that can be seen that Span-80 formation, and filter loss is larger.
【Comparative example 2】
Together【Embodiment 7】, difference is with 3 wt/vol % N, N '-bis- vegetable oil acids acyl group propane diamine(X=3, y=0, z
=0)Substitute 3 wt/vol %N, N '-bis- vegetable oil acids acyl group AEEA polyoxyethylene poly-oxygen propylene aether(X=3, y=3, z
=5)For emulsifying agent, remaining is identical, determines rheological parameter, emulsion-breaking voltage and the API filtration of water-in-oil type drilling fluid system,
As a result it is as shown in table 2.The data of contrast table 1 can be seen that N, the system of N '-bis- vegetable oil acids acyl group propane diamine formation, before aging
Rheological property is poor afterwards, beyond measurement range, and system of the emulsion-breaking voltage also than the emulsifying agent formation of the present invention is low.
【Comparative example 3】
Together【Embodiment 7】, difference is with 3 wt/vol % N, N '-bis- vegetable oil acids acyl group propane diamine polyethenoxy ether
(X=3, y=0, z=3)Substitute 3 wt/vol %N, N '-bis- vegetable oil acids acyl group AEEA polyoxyethylene poly-oxygen propylene aether
(X=3, y=3, z=5)For emulsifying agent, remaining is identical, determine the rheological parameter of water-in-oil type drilling fluid system, emulsion-breaking voltage and
API filtration, as a result as shown in table 2.The data of contrast table 1 can be seen that N, N '-bis- vegetable oil acids acyl group propane diamine polyoxy third
Alkene ether(X=3, y=0, z=3)The system of formation, system yield value, the emulsion-breaking voltage of formation is relatively low, and filter loss is larger.
【Comparative example 4】
Together【Embodiment 7】, difference is with 3 wt/vol % N, N '-bis- vegetable oil acids acyl group propane diamine polyethenoxy ether
(X=3, y=0, z=5)Substitute 3 wt/vol %N, N '-bis- vegetable oil acids acyl group AEEA polyoxyethylene poly-oxygen propylene aether
(X=3, y=3, z=5)For emulsifying agent, remaining is identical, determine the rheological parameter of water-in-oil type drilling fluid system, emulsion-breaking voltage and
API filtration, as a result as shown in table 2.The data of contrast table 1 can be seen that N, N '-bis- vegetable oil acids acyl group propane diamine polyoxy third
Alkene ether(X=3, y=0, z=5)The system of formation, system yield value, the emulsion-breaking voltage of formation is relatively low, and filter loss is larger.
【Comparative example 5】
Together【Embodiment 7】, difference is with 3 wt/vol % INVERMUL emulsifying agents(Halliburton Baroid are public
Department's production)Substitute 3 wt/vol %N, N '-bis- vegetable oil acids acyl group AEEA polyoxyethylene poly-oxygen propylene aether(Y=3, z
=5)For emulsifying agent, remaining is identical, determines rheological parameter, emulsion-breaking voltage and the API filtration of water-in-oil type drilling fluid system,
As a result it is as shown in table 2.The data of contrast table 1 can be seen that the system of INVERMUL formation, and rheological property is poor before and after aging,
Beyond measurement range, system of the emulsion-breaking voltage also than the emulsifying agent formation of the present invention is low.
Table 2
。
Claims (10)
1. a kind of oil base drilling fluid emulsifying agent, its molecular formula is:
Wherein R1For containing C8~C30Saturation or unsaturated alkyl, R2For hydrogen, x=1~10, y=1~40, z=0~40 and z
In 0.
2. oil base drilling fluid emulsifying agent according to claim 1, it is characterised in that described R1Selected from C11~C23It is full
And/or undersaturated alkyl, or C11~C23Saturated hydrocarbyl and unsaturated alkyl mixing alkyl.
3. oil base drilling fluid emulsifying agent according to claim 2, it is characterised in that described R1It is independently selected from carbon number
For 11,13,15,17,19,21 saturated hydrocarbons or unsaturated alkyl, or 11,13,15,17,
19,21 saturated hydrocarbons and the mixing alkyl of unsaturated hydrocarbons.
4. oil base drilling fluid emulsifying agent according to claim 1, it is characterised in that x=2~6, y=1~20, z=0~
30 and z is not equal to 0.
5. oil base drilling fluid emulsifying agent according to claim 4, it is characterised in that x is 2 or 3, y are 1~10.
6. oil base drilling fluid emulsifying agent according to claim 5, it is characterised in that z=0~20 and z is not equal to 0.
7. oil base drilling fluid emulsifying agent according to claim 1, it is characterised in that described oil base drilling fluid emulsification
The preparation method of agent, comprises the following steps:
(a)R1CONH(CH2)xNR2CH2CH2OH preparation
The R in the presence of base catalyst1COOCH3With NH2(CH2)xNHCH2CH2OH reacts 2~24 at a temperature of 80~220 DEG C
Hour, reaction terminates the unreacted raw material of rear vacuum distillation removing and the methanol of generation obtains the R1CONH(CH2)
xNR2CH2CH2OH;Wherein, R1COOCH3With NH2(CH2)xNHCH2CH2OH mol ratio is 1:0.1~6;
(b)R1CONH(CH2)xNR2(CH2CH2O)y-(CH2CHCH3O)zH preparation:
In the presence of base catalyst, the R synthesized by step (a)1CONH(CH2)xNR2CH2CH2OH and required oxirane and
Expoxy propane, which react, obtains described R1CONH(CH2)xNR2(CH2CH2O)y-(CH2CHCH3O)zH。
8. the preparation method of oil base drilling fluid emulsifying agent according to claim 7, it is characterised in that described in step (a)
Base catalyst at least one of for alkali metal hydroxide, alkaline earth metal hydroxide.
9. the preparation method of oil base drilling fluid emulsifying agent according to claim 7, it is characterised in that described in step (b)
Base catalyst at least one of for alkaline earth oxide, alkaline earth metal hydroxide.
10. the preparation method of oil base drilling fluid emulsifying agent according to claim 9, it is characterised in that step (b) it is anti-
It is 85~180 DEG C to answer temperature, and pressure is less than 0.80MPa gauge pressures.
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