CN105441038B - Primary emulsifier and preparation method therefor, emulsifier composition and application thereof, and oil-based drilling fluid - Google Patents
Primary emulsifier and preparation method therefor, emulsifier composition and application thereof, and oil-based drilling fluid Download PDFInfo
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- CN105441038B CN105441038B CN201510082288.6A CN201510082288A CN105441038B CN 105441038 B CN105441038 B CN 105441038B CN 201510082288 A CN201510082288 A CN 201510082288A CN 105441038 B CN105441038 B CN 105441038B
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Abstract
The present invention relates to the field of well drilling, and discloses a primary emulsifier and a preparation method therefor, an emulsifier composition and an application thereof, and oil-based drilling fluid. The primary emulsifier comprises an amide compound and a fatty acid compound; the amide compound comprises at least one amide group, at least one unsaturated double bond, and at least one alkyl containing 14-30 carbon atoms; and the fatty acid compound comprises 20-80 carbon atoms. When the primary emulsifier is used for drilling fluid base mud, the primary emulsifier has a good emulsifying effect and excellent temperature resistance. In addition, the synthetic materials of the primary emulsifier provided by the present invention are widely available and inexpensive, non-fluorescent, and environmentally friendly, and thus the primary emulsifier has great prospects for industrial applications.
Description
Technical field
The present invention relates to a kind of primary emulsion, a kind of preparation method of primary emulsion, the main breast being prepared by the method
Agent, a kind of emulsifier combination, described primary emulsion or emulsifier combination are as the application and of well-drilling liquid emulgent
Plant oil base drilling fluid.
Background technology
With the development of petroleum industry, the strategy that current Deep Oil And Gas Exploration resource has become China takes over the energy, even more at present
With the emphasis in following oil gas increasing the storage.Recently as increasing of deep-well and ultra-deep well drilling quantity, drilling fluid temperature resistance is carried
Go out higher requirement.General water-base drilling fluid can not meet field requirement.And oil base drilling fluid has the excellent of high temperature resistance
Point is gradually taken seriously, and starts to put in a large number application.
Oil base drilling fluid is usually used diesel oil or low toxicity mineral oil as base fluid, is a kind of using saline as discontinuous
This drilling fluid is abroad generally referred to as by the emulsion drilling fluid with oils property being formed after phase, at a certain temperature stirring
Inverse emulsion drilling fluid.Generally, oil ratio in Water-In-Oil drilling fluid all can be more than 70%, so normal referred to as this oil bag
Aqueous drilling fluid is oil base drilling fluid.Because foreign minister is oil phase, oil base drilling fluid has very strong rejection, can stablize well
Wall, prevent from caving in, have good protective value to oil-gas Layer particularly water-sensitive formation.Oil base drilling fluid has anti-height well simultaneously
Warm nature can be with greasy property it is adaptable to deep-well high angle hole be drilled.Water-base drilling fluid relatively, oil base drilling fluid has more preferable suppression
Performance and high temperature resistant property.Oil base drilling fluid also has some shortcomings simultaneously, such as prepares high cost, environment is adversely affected
Deng.What oil base drilling fluid one was main safeguards that difficult point is to keep the stability of emulsion, there is breast in drilling process all the time
Change the danger lost efficacy, particularly when boring deep hot well, high temperature action makes emulsion be easier loss of stability.Wherein, emulsifying agent
It is the key component preparing oil base drilling fluid system, be to ensure that in emulsion system, the dispersion of dispersion phase and longer-term keep
Stable determiner.The good primary emulsion of performance can not only strengthen the temperature resistance of oil base drilling fluid, has under the high temperature conditions
There is more preferable electrical stability, system has more preferable large rock-carrying ability, but also drilling failure can be greatly reduced, improve drilling well effect
Rate.
Content of the invention
It is an object of the invention to provide a kind of new primary emulsion, a kind of preparation method of primary emulsion, by party's legal system
A kind of standby primary emulsion, emulsifier combination, described primary emulsion or the emulsifier combination obtaining is as well-drilling liquid emulgent
Application and a kind of oil base drilling fluid.
Specifically, the primary emulsion that the present invention provides contains amides compound and fatty acid compound, described amide
Class compound contain at least one amide group, at least one unsaturated double-bond and at least one include 14-30 carbon atom
Alkyl, described fatty acid compound includes 20-80 carbon atom.
The preparation method of the primary emulsion that the present invention provides comprises the following steps：
(1) polyamine compounds and the first unsaturated fatty acid are carried out the first amidation process, and by obtain described
The product of monamideization reaction and anhydride and/or polybasic carboxylic acid carry out the second amidation process, obtain component A；
(2) at 150-180 DEG C, by the second unsaturated fatty acid and unsaturated acid anhydride and/or unsaturated polybasic carboxylic acid
Reaction 3-5 hour, obtains component B；
(3) at 60-80 DEG C, by described component A and component B mixing 2-4 hour；
In the preparation process of described component A, the consumption of the polyamine compounds in terms of primary amine group with terms of hydroxy-acid group
The consumption of the first unsaturated fatty acid mol ratio be (1.8-2.2):1, the consumption of the polyamine compounds in terms of primary amine group
Mol ratio with the anhydride counted with anhydride group and total consumption of the polybasic carboxylic acid counted with hydroxy-acid group is (1.8-2.2):1, institute
State the first unsaturated fatty acid to contain at least one unsaturated double-bond and include 14-30 carbon atom；
In the preparation process of described component B, described second unsaturated fatty acid contain at least one unsaturated double-bond and
Including 14-30 carbon atom.
Present invention also offers the primary emulsion being prepared by said method.
The described emulsifier combination that the present invention provides includes above-mentioned primary emulsion and co-emulsifier.
Present invention also offers above-mentioned primary emulsion or emulsifier combination are as the application of well-drilling liquid emulgent.
Additionally, the oil base drilling fluid that the present invention provides contains drilling well liquid-based slurry and emulsifying agent, wherein, described emulsifying agent is upper
State primary emulsion or emulsifier combination.
The present inventor finds after further investigation, the main emulsifying being prepared using the method that the present invention provides
Agent has extraordinary emulsifying effectiveness, can adapt to many oil base drilling fluid systems, all has in most oil base drilling fluid systems
There is preferable temperature resistance stability.Additionally, the synthesis material wide material sources of primary emulsion of present invention offer and cheap, unstressed configuration,
Environmental sound, great prospects for commercial application.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The primary emulsion that the present invention provides contains amides compound and fatty acid compound, described amides compound
Containing at least one amide group, at least one unsaturated double-bond and at least one include the alkyl of 14-30 carbon atom, institute
State fatty acid compound and include 20-80 carbon atom.Preferably, described amides compound contains at least one amide group
And at least one carries unsaturated double-bond and the alkyl of 14-20 carbon atom of inclusion, described fatty acid compound includes 25-
50 carbon atoms.
The present invention is not particularly limited to the content of each component in described primary emulsion, but more excellent in order to obtain
Emulsifying effectiveness is it is preferable that on the basis of the gross weight of described primary emulsion, the content of described amides compound is 60-90 weight
Amount %, the content of described fatty acid compound is 10-40 weight %；It is highly preferred that with the gross weight of described primary emulsion being
Benchmark, the content of described amides compound is 70-85 weight %, and the content of described fatty acid compound is 15-30 weight
Amount %.
As described above, described amides compound contain at least one amide group, at least one unsaturated double-bond and
At least one includes the alkyl of 14-30 carbon atom.Preferably, in addition to above-mentioned group, described amides compound also contains
There is at least one secondary amine group, in the present invention, described secondary amine group does not include the secondary amine in amide group.It is highly preferred that institute
At least one unsaturated double-bond stating amides compound is present in including in the alkyl of 14-30 carbon atom.
Described amides compound can be commercially available it is also possible to according to well known to a person skilled in the art various side
Method prepares.Preferably, described amides compound prepares in accordance with the following methods：By polyamine compounds and the first insatiable hunger
Carry out the first amidation process with fatty acid, then by the product of described first amidation process and anhydride and/or polybasic carboxylic acid
Carry out the second amidation process, and the polyamine compounds in the preparation process of described amides compound, in terms of primary amine group
Consumption be (1.8-2.2) with the mol ratio of the consumption of the first unsaturated fatty acid counted with hydroxy-acid group:1, with primary amine group
The consumption of polyamine compounds of meter is rubbed with total consumption of the anhydride in terms of anhydride group and the polybasic carboxylic acid in terms of hydroxy-acid group
Your ratio is (1.8-2.2):1, described first unsaturated fatty acid contains at least one unsaturated double-bond and 14-30 carbon of inclusion is former
Son.
Described polyamine compounds refer to the compound of at least two primary amine groups.Preferably, described polyamine compounds
In addition to containing at least two primary amine groups, also contain at least one secondary amine group.From the point of view of raw material is ready availability, institute
State at least one that polyamine compounds are preferably in ethylenediamine, diethylenetriamine, TEPA and m-diaminobenzene..
In the above-mentioned preparation process of described amides compound, polyamine compounds and the first unsaturated fatty acid and acid
Acid anhydride and/or polybasic carboxylic acid carry out amidation process and generate at least one amido link, and the first unsaturated fatty acid provides at least
One unsaturated double-bond and the alkyl that includes 14-30 carbon atom so as to get amides compound contain at least one amide
Group and with least one unsaturated double-bond and include 14-30 carbon atom alkyl.
Described first unsaturated fatty acid can for existing various with least one unsaturated double-bond and include 14-30
Individual carbon atom, preferably include the fatty acid of 14-20 carbon atom, from the point of view of raw material is ready availability, described first is unsaturated
Fatty acid is preferably Palmic acid, at least one in linoleic plus oleic acid.The species of described anhydride can also be the normal of this area
Rule select, from the point of view of raw material is ready availability, described anhydride preferably acetic anhydride, cis -3,6- methylene -1, and 2,3,6-
At least one in tetrabydrophthalic anhydride (carbic anhydride), methylnadic anhydride, succinic anhydride and maleic anhydride.Institute
The species stating polybasic carboxylic acid can also be the conventional selection of this area, from the point of view of raw material is ready availability, described polybasic carboxylic acid
It is preferably at least one in malonic acid, ethanedioic acid, succinic acid, tricarballylic acid and 2- hydroxy propane -1,2,3- tricarboxylic acids.
The present invention is all not particularly limited to the condition of described first amidation process and the second amidation process.Example
As the condition of the first amidation process generally includes reaction temperature and can be 220-230 DEG C, and pH value can be 7-9, the response time
It can be 3-5 hour；The condition of the second amidation process generally includes reaction temperature and can be 75-90 DEG C, and pH value can be 7-
9, the response time can be 6-10 hour.
According to a kind of specific embodiment of the present invention, described amides compound prepares in such a way：?
Under room temperature, polyamine compounds and the mixing of the first unsaturated fatty acid stir 20-30min, so under low speed 80-100r/min
Afterwards the pH value of the mixture obtaining is adjusted to 7-9, then using oil bath, this mixture is heated to 220-230 DEG C, adopts simultaneously
With dividing a water score water, temperature is reacted 3-5 hour at maintaining 220-230 DEG C, is cooled to room temperature afterwards, obtains " incomplete acyl
Amine "；Then at normal temperatures, " incomplete amide " is mixed with anhydride and/or polybasic carboxylic acid, then mixed by obtain using water-bath
Compound is heated to 75-90 DEG C, stirs 6-10 hour under 200-500r/min.
Described fatty acid compound can be commercially available it is also possible to prepare according to various methods well known in the art
Obtain.Preferably, described fatty acid compound prepares in accordance with the following methods：At 150-180 DEG C, unsaturated by second
Fatty acid and unsaturated acid anhydride and/or unsaturated polybasic carboxylic acid reaction 3-5 hour, described second unsaturated fatty acid contain to
A few unsaturated double-bond and 14-30 carbon atom of inclusion.
In the above-mentioned preparation process of described fatty acid compound, the second unsaturated fatty acid and unsaturated acid anhydride
And/or there is additive reaction and/or the second unsaturated fatty acid and unsaturation in the unsaturated double-bond in unsaturation polybasic carboxylic acid
There is condensation reaction, thus forming fatty acid compound between anhydride and/or unsaturated polybasic carboxylic acid.
The present invention is to the species of described second unsaturated fatty acid and unsaturated acid anhydride and unsaturated polybasic carboxylic acid and use
Amount is not particularly limited.For example, described second unsaturated fatty acid can be existing various unsaturated with least one
Double bond and include 14-30 carbon atom, preferably include the fatty acid of 14-20 carbon atom, from the point of view of raw material is ready availability,
Described second unsaturated fatty acid is preferably Palmic acid, at least one in linoleic plus oleic acid.Described unsaturated acid anhydride is permissible
For the existing anhydride with unsaturated double-bond, from the point of view of raw material is ready availability, described unsaturated acid anhydride preferably receives enlightening
At least one in gram anhydride, methylnadic anhydride and maleic anhydride.Described unsaturation polybasic carboxylic acid can be existing each
Plant the polybasic carboxylic acid with unsaturated double-bond, from the point of view of raw material is ready availability, described unsaturation polybasic carboxylic acid is particularly preferred
For maleic acid.Additionally, the consumption of described second unsaturated fatty acid and unsaturated acid anhydride and unsaturated polybasic carboxylic acid is total
The weight ratio of consumption can be (1.5-4):1, preferably (2-4):1.
The preparation method of the primary emulsion that the present invention provides comprises the following steps：
(1) polyamine compounds and the first unsaturated fatty acid are carried out the first amidation process, and by obtain described
The product of monamideization reaction and anhydride and/or polybasic carboxylic acid carry out the second amidation process, obtain component A (containing amide-type
Compound)；
(2) at 150-180 DEG C, by the second unsaturated fatty acid and unsaturated acid anhydride and/or unsaturated polybasic carboxylic acid
Reaction 3-5 hour, obtains component B (containing fatty acid compound)；
(3) at 60-80 DEG C, by described component A and component B mixing 2-4 hour；
In the preparation process of described component A, the consumption of the polyamine compounds in terms of primary amine group with terms of hydroxy-acid group
The consumption of the first unsaturated fatty acid mol ratio be (1.8-2.2):1, the consumption of the polyamine compounds in terms of primary amine group
Mol ratio with the anhydride counted with anhydride group and total consumption of the polybasic carboxylic acid counted with hydroxy-acid group is (1.8-2.2):1, institute
State the first unsaturated fatty acid to contain at least one unsaturated double-bond and include 14-30 carbon atom；
In the preparation process of described component B, described second unsaturated fatty acid contain at least one unsaturated double-bond and
Including 14-30 carbon atom.
Described polyamine compounds refer to the compound of at least two primary amine groups.Preferably, described polyamine compounds
In addition to containing at least two primary amine groups, also contain at least one secondary amine group.From the point of view of raw material is ready availability, institute
State at least one that polyamine compounds are preferably in ethylenediamine, diethylenetriamine, TEPA and m-diaminobenzene..
Described first unsaturated fatty acid can for existing various with least one unsaturated double-bond and include 14-30
Individual carbon atom, preferably include the fatty acid of 14-20 carbon atom, from the point of view of raw material is ready availability, described first is unsaturated
Fatty acid is preferably Palmic acid, at least one in linoleic plus oleic acid.The species of described anhydride can also be the normal of this area
Rule select, from the point of view of raw material is ready availability, described anhydride preferably acetic anhydride, cis -3,6- methylene -1, and 2,3,6-
At least one in tetrabydrophthalic anhydride (carbic anhydride), methylnadic anhydride, succinic anhydride and maleic anhydride.Institute
The species stating polybasic carboxylic acid can also be the conventional selection of this area, from the point of view of raw material is ready availability, described polybasic carboxylic acid
It is preferably at least one in malonic acid, ethanedioic acid, succinic acid, tricarballylic acid and 2- hydroxy propane -1,2,3- tricarboxylic acids.
The present invention is all not particularly limited to the condition of described first amidation process and the second amidation process.Example
As the condition of the first amidation process generally includes reaction temperature and can be 220-230 DEG C, and pH value can be 7-9, the response time
It can be 3-5 hour；The condition of the second amidation process generally includes reaction temperature and can be 75-90 DEG C, and pH value can be 7-
9, the response time can be 6-10 hour.
According to a kind of specific embodiment of the present invention, described component A prepares in such a way：At normal temperatures,
By polyamine compounds and the mixing of the first unsaturated fatty acid, stir 20-30min under low speed 80-100r/min, then will obtain
The pH value of mixture adjust to 7-9, then using oil bath, this mixture is heated to 220-230 DEG C, simultaneously using a point water meter
Divide water, temperature reacts 3-5 hour at maintaining 220-230 DEG C, is cooled to room temperature afterwards, obtains " incomplete amide "；Then exist
Under room temperature, " incomplete amide " is mixed with anhydride and/or polybasic carboxylic acid, then using water-bath, the mixture obtaining is heated to
75-90 DEG C, stir 6-10 hour under 200-500r/min.
The present invention is to the species of described second unsaturated fatty acid and unsaturated acid anhydride and unsaturated polybasic carboxylic acid and use
Amount is not particularly limited.For example, described second unsaturated fatty acid can be existing various unsaturated with least one
Double bond and include 14-30 carbon atom, preferably include the fatty acid of 14-20 carbon atom, from the point of view of raw material is ready availability,
Described second unsaturated fatty acid is preferably Palmic acid, at least one in linoleic plus oleic acid.Described unsaturated acid anhydride is permissible
For the existing anhydride with unsaturated double-bond, from the point of view of raw material is ready availability, described unsaturated acid anhydride preferably receives enlightening
At least one in gram anhydride, methylnadic anhydride and maleic anhydride.Described unsaturation polybasic carboxylic acid can be existing each
Plant the polybasic carboxylic acid with unsaturated double-bond, from the point of view of raw material is ready availability, described unsaturation polybasic carboxylic acid is particularly preferred
For maleic acid.Additionally, the consumption of described second unsaturated fatty acid and unsaturated acid anhydride and unsaturated polybasic carboxylic acid is total
The weight ratio of consumption can be (1.5-4):1, preferably (2-4):1.
The preparation method of the primary emulsion being provided according to the present invention, in step (3), the weight ratio of described component A and component B
Can be (1.5-9):1, preferably (2.5-5):1.
Present invention also offers the primary emulsion being prepared by said method.Although the present invention verifies not over characterizing
Cross the component of the primary emulsion being obtained by said method, but can be deduced in described primary emulsion according to reaction mechanism and contain
Described amides compound and described fatty acid compound.
Additionally, present invention also offers a kind of emulsifier combination, described emulsifier combination includes primary emulsion and helps
Emulsifying agent, wherein, described primary emulsion is above-mentioned primary emulsion.
In described emulsifier combination, described primary emulsion can be (2-5) with the weight ratio of co-emulsifier:1, preferably
For (2.5-4):1.Additionally, the species of described co-emulsifier can be the conventional selection of this area, for example, it is possible to it is polyamide-based
Co-emulsifier, specially those skilled in the art all can know, therefore not to repeat here.
Present invention also offers above-mentioned primary emulsion or emulsifier combination are as the application of well-drilling liquid emulgent.
The oil base drilling fluid that the present invention provides contains drilling well liquid-based slurry and emulsifying agent, and wherein, described emulsifying agent is above-mentioned master
Emulsifying agent or emulsifier combination.
The present invention is not particularly limited to the consumption of described emulsifying agent, generally should be entered according to the consumption of drilling well liquid-based slurry
Row selects, and for example, with respect to the drilling well liquid-based slurry of 100 weight portions, the consumption of described emulsifying agent can be 0.5-5 weight portion, excellent
Elect 1.5-3 weight portion as.
Mainly the theing improvement is that of oil base drilling fluid that the present invention provides provides a kind of new emulsifying agent, and drilling fluid
The species of base slurry and concrete component can be all that the conventional of this area selects, and this those skilled in the art all can be known, here
Do not repeat.
Hereinafter will be described the present invention by embodiment.
Embodiment 1
This embodiment is used for the preparation method of the primary emulsion of present invention offer is described.
(1) by reactant diethylenetriamine in molar ratio under room temperature:Oleic acid=1:1 (i.e. divinyl in terms of primary amine group
The consumption of triamine is 2 with the mol ratio of the consumption of the Oleic acid counted with hydroxy-acid group:1) mix, and stir under 250r/min
20min, then adjusts the pH value of the mixture obtaining to 7, then using oil bath, this mixture is heated to 225 DEG C, simultaneously
Using a point water score water, and temperature is maintained reaction 5 hours at 225 DEG C, be cooled to room temperature, obtain intermediate product " not exclusively
Amide ".
Under room temperature, " incomplete amide " is mixed with oxalic acid (consumption of the diethylenetriamine in terms of primary amine group with carboxylic acid
The mol ratio of the consumption of the oxalic acid of group meter is 2:1), then the pH value of the mixture obtaining is adjusted to 7, then heating in water bath
To 75 DEG C, and stirring reaction 10h under the speed of 500r/min, obtain product A.Through infrared detection, in product A, contain amide groups
Group and unsaturated double-bond.
(2) under room temperature by Oleic acid and carbic anhydride according to 3:1 weight is than mixing, and stirs under the speed of 250r/min
Mix 20min, then using oil bath, the mixture obtaining is heated to 150 DEG C, and react 5 hours at such a temperature, cool down afterwards
To room temperature, obtain product B.
(3) under room temperature by product A and product B according to 4:1 weight is than mixing, and stirs 30 minutes under 300r/min,
Then heating in water bath, to 60 DEG C of stirring reactions 4h, obtains primary emulsion R1.
Embodiment 2
This embodiment is used for the preparation method of the primary emulsion of present invention offer is described.
(1) by reactant TEPA in molar ratio under room temperature:Linoleic acid=1:1 (i.e. tetrem in terms of primary amine group
The mol ratio of the consumption of alkene five amine and the linoleic consumption counted with hydroxy-acid group is for 2:1) mix, and stir under 250r/min
40min, then adjusts the pH value of the mixture obtaining to 9, then using oil bath, this mixture is heated to 230 DEG C, simultaneously
Using a point water score water, and temperature is maintained reaction 3 hours at 230 DEG C, be cooled to room temperature, obtain intermediate product " not exclusively
Amide ".
Under room temperature, " incomplete amide " is mixed with malonic acid (consumption of the TEPA in terms of primary amine group with carboxylic
The mol ratio of the consumption of the malonic acid of acid groups meter is 2:1), then the pH value of the mixture obtaining is adjusted to 8, then water-bath
It is heated to 90 DEG C, and stirring reaction 6h under the speed of 400r/min, obtain product A.Through infrared detection, in product A, contain acyl
Amine groups and unsaturated double-bond.
(2) under room temperature by linoleic acid and methylnadic anhydride according to 4:1 weight is than mixing, and the speed in 250r/min
Degree is lower to stir 40min, then using oil bath, the mixture obtaining is heated to 180 DEG C, and reacts 3 hours at such a temperature, it
After be cooled to room temperature, obtain product B.
(3) under room temperature by product A and product B according to 5:1 weight is than mixing, and stirs 30 minutes under 300r/min,
Then heating in water bath, to 80 DEG C of stirring reactions 2h, obtains primary emulsion R2.
Embodiment 3
This embodiment is used for the preparation method of the primary emulsion of present invention offer is described.
(1) by reactant ethylenediamine in molar ratio under room temperature:Palmic acid=1:1 (i.e. ethylenediamine in terms of primary amine group
Consumption is 2 with the mol ratio of the consumption of the Palmic acid counted with hydroxy-acid group:1) mix, and stir 20min under 250r/min, so
Afterwards the pH value of the mixture obtaining is adjusted to 8, then using oil bath, this mixture is heated to 227 DEG C, simultaneously using a point water
Score water, and temperature is maintained reaction 4 hours at 227 DEG C, it is cooled to room temperature, obtain intermediate product " incomplete amide ".
Under room temperature, " incomplete amide " is mixed with maleic anhydride (consumption of the ethylenediamine in terms of primary amine group with anhydride
The mol ratio of the consumption of the maleic anhydride of group meter is 2:1), then the pH value of the mixture obtaining is adjusted to 9, then water-bath
It is heated to 80 DEG C, and stirring reaction 8h under the speed of 500r/min, obtain product A.Through infrared detection, in product A, contain acyl
Amine groups and unsaturated double-bond.
(2) under room temperature by linoleic acid and maleic anhydride according to 4:1 weight is than mixing, and stirs under the speed of 250r/min
Mix 20min, then using oil bath, the mixture obtaining is heated to 170 DEG C, and react 4 hours at such a temperature, cool down afterwards
To room temperature, obtain product B.
(3) under room temperature by product A and product B according to 2.5:1 weight is than mixing, and stirs 30 points under 300r/min
Clock, then heating in water bath to 70 DEG C of stirring reactions 3h, obtain primary emulsion R3.
Test case
Test case is used for the test of primary emulsion performance is described.
(1) outward appearance：
The outward appearance of the primary emulsion R1-R3 that each embodiment that detects by an unaided eye under the conditions of natural light is obtained, acquired results are such as
Shown in table 1.
(2) density：
According to GB/T 16783.1-2006《Industrial gas oil drilling fluid on-the-spot test part 2：Oil base drilling fluid》
Specified in method and using drilling fluid density meter (purchased from Wei Ku instrument and meter company, model YM) measure primary emulsion R1-
The density of R3, acquired results are as shown in table 1.
(3) emulsifying agent stability：
1. the configuration of drilling well liquid-based slurry：
Respectively according to three kinds of oil base drilling fluid base slurries of following components proportioning：
Base slurry I -- diesel oil base drilling fluid base is starched：The CaCl that diesel oil and concentration are 30 weight %2Aqueous solution is according to 85:15
Weight than mix homogeneously, be subsequently adding consumption be diesel oil and CaCl2The organoclay of 1 weight % of the total consumption of aqueous solution (is purchased from
Fine Chemical Co., Ltd is shone in Shanghai ten thousand, the trade mark be HCC, similarly hereinafter) and consumption be diesel oil and CaCl2The 1 of the total consumption of aqueous solution
The CaO of weight % mix homogeneously；
Base slurry II -- white oil base drilling fluid base is starched：The CaCl that white oil and concentration are 30 weight %2Aqueous solution is according to 85:15
Weight than mix homogeneously, be subsequently adding consumption be white oil and CaCl2The organoclay of 1 weight % of the total consumption of aqueous solution and use
Measure as white oil and CaCl2The CaO of 1 weight % of the total consumption of aqueous solution mix homogeneously；
Base slurry III -- no native phase oil base drilling fluid：The CaCl that white oil and concentration are 30 weight %2Aqueous solution is according to 85:15
Weight than mix homogeneously, be subsequently adding consumption be white oil and CaCl2Extracting and cutting agent (the China of 1 weight % of the total consumption of aqueous solution
Petroleum Univ. produce, the trade mark be CFZTQ-1) and consumption be white oil and CaCl21 weight % of the total consumption of aqueous solution
CaO mix homogeneously.
2. the test of aging emulsification rate in front and back：
Take 300mL above-mentioned three kinds of bases slurry to be placed in 500mL graduated cylinder respectively, be then respectively adding consumption and starch total consumption for base
The primary emulsion R1-R3 of 3 volumes %, primary emulsion R1 and polyacrylamide co-emulsifier (polyacrylamide co-emulsifier
Purchased from Pingxiang City Bo Xin Industrial Co., Ltd., the trade mark is PAM-ASG-700, similarly hereinafter) compare 2 according to weight:1 mixture, commercially available
Primary emulsion EZ-MUL (purchased from Halliburton Company, main component includes：Modified fat acid, partial amides surfactant,
Similarly hereinafter) and VER-MUL (purchased from Mike Bagong department, main component includes：Unsaturated tallow amide, unsaturated fatty acid, similarly hereinafter),
Obtain water-in-oil emulsion mud after stirring, then this water-in-oil emulsion mud is stood 16 hours, respectively on measurement base slurry
Lower volume, and calculate emulsification rate (R according to below equationK)：
Wherein：RK-- emulsification rate；
K0-- cumulative volume after 16 hours for the base slurry standing；
K1-- the volume on base slurry standing upper strata after 16 hours.
By above-mentioned water-in-oil emulsion mud aging 16 hours at 150 DEG C, then stir and stand 16 hours, respectively
Measurement base starches levels volume, and calculates the emulsification rate (R of the water-in-oil emulsion mud after aging according to above formulaK).Institute
Obtain result as shown in table 2.
3. the test of aging electrical stability in front and back：
Take 200mL above-mentioned three kinds of bases slurry respectively, be then respectively adding the main emulsifying that consumption starches 3 volumes % of total consumption for base
Agent R1-R3, primary emulsion R1 and polyacrylamide co-emulsifier compare 2 according to weight:1 mixture, commercially available primary emulsion
EZ-MUL and VER-MUL, then uses blender high-speed stirred 20min under the conditions of 3000r/min, obtains Water-In-Oil emulsifying mud
Slurry, is then passed through electric current toward in water-in-oil emulsion mud, and (public purchased from Qingdao Jiaonan Analytical Instruments Plant with electrical stability tester
Department, model D90-300, similarly hereinafter) measure emulsion-breaking voltage respectively.Described emulsion-breaking voltage refers to that water-in-oil emulsion mud starts to destroy
When voltage.Emulsion-breaking voltage can reflect the electrical stability of water-in-oil emulsion mud, and emulsion-breaking voltage is big to represent holding mud emulsifying
The scope of state is big, has preferable stability；And the little less stable then representing mud of emulsion-breaking voltage.In test process,
Electrode is inserted in tested emulsion mud, selects applicable stepping voltage dupler, be gradually increased the voltage at electrode two ends,
It is destroyed until electrical stability tester shows emulsion mud, writes down voltage readings when starting to destroy, voltage value is higher, oil
The stability of bag water emulsification mud is better.
By above-mentioned water-in-oil emulsion mud aging 16 hours at 150 DEG C, then again toward the Water-In-Oil emulsifying after aging
It is passed through electric current in mud, and measure emulsion-breaking voltage respectively with electrical stability tester.Acquired results are as shown in table 2.
4. apparent viscosity (AV) before and after aging, plastic viscosity (PV), shear force (YP) ,/survey of egress (G10 "/10 ') of ingressing
Examination, acquired results are as shown in table 3：
I () apparent viscosity (AV) is calculated as follows and obtains：
Wherein, Φ600By being surveyed reading using six fast rotating cylinder viscometers under rotating speed is by 600r/min；
(ii) PV is plastic viscosity (plastic viscosity), is calculated as follows and obtains：
PV=Φ600-Φ300
Wherein, Φ600By the reading surveyed under rotating speed is by 600r/min using six fast rotating cylinder viscometers, Φ300It is employing
The reading that six fast rotating cylinder viscometers are surveyed under rotating speed is by 300r/min；
(iii) YP is shear force (yield point), is calculated as follows and obtains：
YP=0.48 (Φ300-PV)
Wherein, Φ300By the reading surveyed under rotating speed is by 300r/min using six fast rotating cylinder viscometers, PV is that plasticity is viscous
Degree；
(iiii) drilling fluid is stirred quiet after 1min under rotating speed is for 600r/min by finger of ingressing using six fast rotating cylinder viscometers
Put 10s, and the reading surveyed under rotating speed is by 3r/min；
Egress refers under rotating speed is for 600r/min, drilling fluid be stirred standing after 1min using six fast rotating cylinder viscometers
10min, and be measured reading under 3r/min in rotating speed.
Table 1
| Numbering | Primary emulsion | Outward appearance | Density (g/cm3) |
| Embodiment 1 | R1 | Pitchy emulsion | 1.02 |
| Embodiment 2 | R2 | Pitchy emulsion | 1.02 |
| Embodiment 3 | R3 | Pitchy emulsion | 1.02 |
Table 2
Note：In table 2,3vt% accounts for the percentage ratio of base volume of slurry for primary emulsion volume.
Table 3
As can be seen from the above results, drilling well liquid-based is used for using the primary emulsion that the method that the present invention provides prepares
During slurry, before ageing after be all obtained in that higher emulsification rate and emulsion-breaking voltage it can be seen that, it has preferable emulsifying effectiveness
With preferable temperature resistance stability.Additionally, the synthesis material wide material sources of primary emulsion of present invention offer and cheap, unstressed configuration,
Environmental sound, great prospects for commercial application.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy no longer separately illustrates.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (10)
1. a kind of preparation method of primary emulsion, the method comprises the following steps：
(1) polyamine compounds and the first unsaturated fatty acid are carried out the first amidation process, and by described first acyl obtaining
The product of aminating reaction carries out the second amidation process with anhydride and/or polybasic carboxylic acid, obtains component A；Described first amidatioon
The temperature of reaction is 220-230 DEG C；The temperature of the second amidation process is 75-90 DEG C；Wherein, described polyamine compounds are second two
At least one in amine, diethylenetriamine, TEPA and m-diaminobenzene.；Described anhydride is acetic anhydride, carbic anhydride, first
At least one in base carbic anhydride, succinic anhydride and maleic anhydride；Described polybasic carboxylic acid is malonic acid, ethanedioic acid, fourth two
At least one in acid, tricarballylic acid and 2- hydroxy propane -1,2,3- tricarboxylic acids；
(2) at 150-180 DEG C, by the second unsaturated fatty acid and unsaturated acid anhydride and/or unsaturated polybasic carboxylic acid reaction
3-5 hour, obtains component B；Described unsaturated acid anhydride is carbic anhydride, in methylnadic anhydride and maleic anhydride at least
A kind of；Described unsaturation polybasic carboxylic acid is maleic acid；
(3) at 60-80 DEG C, by described component A and component B mixing 2-4 hour；Wherein, the weight of described component A and component B
Than for (1.5-9):1；
In the preparation process of described component A, the consumption of the polyamine compounds in terms of primary amine group and in terms of hydroxy-acid group
The mol ratio of the consumption of one unsaturated fatty acid is (1.8-2.2):1, the consumption of the polyamine compounds in terms of primary amine group with
The mol ratio of total consumption of the anhydride of anhydride group meter and the polybasic carboxylic acid counted with hydroxy-acid group is (1.8-2.2):1；
The species of described first unsaturated fatty acid and the second unsaturated fatty acid is identical or different, and is each independently Petiolus Trachycarpi
At least one in acid, linoleic plus oleic acid.
2. method according to claim 1, wherein, in step (1), the condition of described first amidation process includes pH value
For 7-9, the response time is 3-5 hour；It is 7-9 that the condition of the second amidation process includes pH value, and the response time is 6-10 hour.
3. method according to claim 1 and 2, wherein, in step (2), the consumption of described second unsaturated fatty acid with
The weight ratio of total consumption of unsaturated acid anhydride and unsaturated polybasic carboxylic acid is (1.5-4):1.
4. method according to claim 1, wherein, in step (3), described component A is (2.5- with the weight ratio of component B
5):1.
5. the primary emulsion that the method described in any one in claim 1-4 prepares.
6. a kind of emulsifier combination, described emulsifier combination includes primary emulsion and co-emulsifier it is characterised in that described
Primary emulsion is at least one in the primary emulsion described in claim 5.
7. emulsifier combination according to claim 6, wherein, described primary emulsion with the weight ratio of co-emulsifier is
(2-5):1.
8. the primary emulsion described in claim 5 or the emulsifier combination described in claim 6 or 7 are as well-drilling liquid emulgent
Application.
9. a kind of oil base drilling fluid, described oil base drilling fluid contains drilling well liquid-based slurry and emulsifying agent it is characterised in that described emulsifying
Agent is the primary emulsion described in claim 5 or the emulsifier combination described in claim 6 or 7.
10. oil base drilling fluid according to claim 9, wherein, with respect to the drilling well liquid-based slurry of 100 weight portions, described breast
The consumption of agent is 0.5-5 weight portion.
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| CN105885807A (en) * | 2016-04-19 | 2016-08-24 | 潍坊天福化学科技有限公司 | High-temperature-resistant emulsifier for drilling and preparation method of high-temperature-resistant emulsifier |
| US9790417B1 (en) * | 2016-05-20 | 2017-10-17 | China University Of Petroleum (Beijing) | High-density water-based drilling fluid suitable for horizontal shale gas wells |
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| CN108467483B (en) * | 2018-03-27 | 2020-05-22 | 中国石油大学(华东) | Copolymer and application thereof, oil-based drilling fluid stabilizer and preparation method thereof, and oil-based drilling fluid |
| CN109097005B (en) * | 2018-08-09 | 2021-06-04 | 大庆市北华化工厂 | Oil-based drilling fluid emulsifier |
| CN109266319B (en) * | 2018-09-27 | 2021-03-30 | 中国石油天然气股份有限公司 | Full-oil-based drilling fluid and preparation method and application thereof |
| CN113969151B (en) * | 2020-07-22 | 2023-05-02 | 中石化石油工程技术服务有限公司 | Biomass main emulsifier, preparation method and application thereof |
| CN114736381A (en) * | 2022-04-20 | 2022-07-12 | 无锡颐景丰科技有限公司 | Comb-shaped high-molecular surfactant and synthesis method thereof |
| CN114806520B (en) * | 2022-05-30 | 2023-06-06 | 长江大学 | Preparation method of cutting agent for oil-based drilling fluid |
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