CN109111906A - A kind of emulsifying and viscosity-reducing agent for condensed oil - Google Patents
A kind of emulsifying and viscosity-reducing agent for condensed oil Download PDFInfo
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Abstract
The invention discloses a kind of emulsifying and viscosity-reducing agent for condensed oil, it is made of nonionic surfactant, cationic oligo surfactant, high molecular polymer and water, the cationic oligo surfactant, selected from structural formula compound represented in formula (I), wherein, R C4~C18Alkyl；X is selected from F‑、Cl‑、Br‑、I‑One or more of.Emulsifying pour depressor of the invention, it is strong to reduce oil water interfacial tension ability, has preferable viscosity reduction and emulsifying effectiveness to viscous crude, is particularly suitable for high-content wax viscous crude, and salt-resistance is strong, low using concentration, cost is relatively low, and when use is not required to plus alkali, is suitable for the quick stratum of alkali.
Description
Technical field
The present invention relates to a kind of emulsifying and viscosity-reducing agent for condensed oil, and in particular to one kind contains certain cationic type oligomeric surface activity
The emulsifying and viscosity-reducing agent for condensed oil of agent.
Background technique
Reducing viscosity by emulsifying technology is versatile and flexible, strong etc. to environmental suitability with field conduct strong operability, technology because of it
Feature becomes the common technology of current heavy crude producing.The technology mainly passes through emulsifying pour depressor in the absorption of oil-water interfaces, drop
Low oil water interfacial tension is greatly lowered viscous so that viscous crude is changed into oil-in-water emulsion from the emulsified state of Water-In-Oil
Degree realizes normal exploitation.
In recent years, the specific gravity that thickened oil recovery accounts for whole oil exploitation gradually increases, geological conditions also increasingly complex, emulsification
The using effect of thinner is influenced by viscous crude physical property and formation condition, and complicated formation condition increases the dosage of emulsifier
Add, viscosity reducing effect phase strain differential even fails, and cost is caused to increase substantially.Under normal circumstances, can all add in emulsifying pour depressor
Enter alkali, to reduce the dosage of applying surface activating agent, but is not particularly suited for the quick stratum of alkali.On the other hand, existing emulsified viscous oil
Thinner, which mainly forms, to be formed mostly with anionic surfactant, nonionic surfactant and cosurfactant etc., this
Class emulsifying pour depressor adaptation common heavy oil and super-viscous oil system, the viscosity reducing effect having had, but for the special viscous crude of high-content wax
Bad adaptability, and it is not suitable for the thick-oil emulsified adhesive-reducing of high calcium-containing magnesium ion water flooding.Therefore, need at present it is a kind of have be directed to
Property reduce the viscosity of high-content wax viscous crude, and salt-resistance high (including calcium ions and magnesium ions), it is lower using concentration, without plus alkali, Neng Goushi
The emulsifying and viscosity-reducing agent for condensed oil of the advantages that stratum quick for alkali.
CN102618245A discloses a kind of novel emulsion thinner, it is mixed by the raw material of following weight proportion
: 63~65 parts of petroleum sulfonate, 9~15 parts of anionic surfactant, 20~30 parts of pH value adjustment agent, the pH value adjustment
Agent be caustic soda with water according to weight for 50:50 is mixed and is made.It is big to be applicable in viscous crude range, is not only suitable for viscosity and is lower than
The viscous crude of 2400mPa.s, be also applied for viscosity be higher than 2400mPa.s viscous crude, and have anti-rock salt ability it is strong, can make viscous crude from
The advantages such as the emulsified state of Water-In-Oil is changed into oil-in-water emulsion, and the viscosity of thickened oil after emulsification is low, and emulsification cost is low.Thinner group
At including dodecyl sodium sulfate, sulfonate type anionic surfactant, alkyl benzene sulphonate salt form anionic surfactant
It is formed with carboxylic acid type anionic surfactant.The thinner can be realized under the conditions of salinity 20000mg/L to common heavy oil
With super-viscous oil reducing viscosity by emulsifying.
CN106032466A discloses a kind of emulsifying and viscosity-reducing agent for condensed oil, composition include nonionic surface active agent, yin from
Subtype oligo surfactant, alcohol and water, the thinner viscous crude high to super special thick oil and bitumen content have preferable viscosity reduction
Effect is suitable for salinity 50000mg/L, but calcium ions and magnesium ions concentration is not more than the mineralized water of 2000mg/L.On the other hand, the drop
Stick is low, at low cost using concentration, when use without plus alkali.
CN 106398675A discloses a kind of emulsifying pour depressor, the emulsifying pour depressor contain cationic surfactant,
Nonionic surfactant, pure and mild high molecular polymer.It also discloses the preparation method of emulsifying pour depressor and is dropped in emulsified viscous oil
Application in viscous.Also disclose the method that thick-oil emulsified adhesive-reducing is carried out using emulsifying pour depressor of the invention.Emulsification of the invention
Thinner can be effectively reduced the viscosity of viscous crude, be particularly suitable for high-content wax viscous crude, can also be applied to the low common heavy oil of the content of wax
And super-viscous oil, and there is fabulous adaptability for the viscous crude of the water flooding containing high calcium and magnesium ion.Its cationic surface used
Activating agent is selected from trimethyl ammonium chloride, tetradecyltrimethylammonium ammonium chloride, cetyl trimethyl ammonium chloride, 18
Alkyltrimethyl ammonium chloride, but need that alcohol is added in compound system, when alcohol content is low, viscosity reducing effect decline.
Summary of the invention
For the above-mentioned prior art, the present invention provides a kind of emulsifying and viscosity-reducing agent for condensed oil, and the thinner is to high-content wax viscous crude
With good viscosity reducing effect.And salt-resistance is high (calcic magnesium ion), can reach under lower concentration conditions and single-stranded surface
The similar viscosity reducing effect of activating agent, it is at low cost, when use without plus alkali, be suitable for the quick stratum of alkali.
The present invention is achieved by the following technical solutions:
A kind of emulsifying and viscosity-reducing agent for condensed oil, by nonionic surfactant, cationic oligo surfactant, polyphosphazene polymer
Close object and water composition, wherein nonionic surfactant accounts for 0.01%~1%, and cationic oligo surfactant accounts for
0.02%~3%, high molecular polymer accounts for 0.01%~1%, and surplus is water, by weight.
The nonionic surface active agent is selected from alkylphenol-polyethenoxy base ether and/or alkylol polyoxyethylene base ether.
The cationic oligo surfactant is selected from one or both of compound A, compound B, compound C
More than；The compound A, compound B, compound C structural formula respectively as shown in (a) (b) (c) in formula (I)；In formula (I), R
For C4~C18Alkyl, preferably C8~C16Alkyl；X is selected from F-、Cl-、Br-、I-One or more of.
Three kinds of compounds of structure shown in formula (I) are laboratory self-control, and preparation method is the synthesis side in following documents
Method (Preparation, Characterization and Properties of Novel Cationic Gemini
Surfactants with Rigid Amido Spacer Groups.J.Surfactants Deterg.2016,19(1):
91-99).Specifically using DL-malic acid dimethyl ester, trimethyl citrate or ethylenediamine tetra-acetic acid as primary raw material, by two
Step reaction, with the synthesis of higher yield.
The high molecular polymer is selected from polyacrylamide, xanthan gum, hydroxypropyl guar, carboxymethyl cellulose, polyethylene
One or more of alcohol.
Further, the degree of polymerization of the alkylphenol-polyethenoxy base ether and/or alkylol polyoxyethylene base ether be 3~
30, alkyl chain length is 6~20.For example, the nonylphenol polyoxyethylene ether series that Jiangsu Hai'an petrochemical plant can be selected to produce
The series of products such as NP-7, NP-10, NP-15 or fatty alcohol polyoxyethylene ether AEO-7, AEO-9, AEO-13.
Preferably, the viscosity average molecular weigh of the polyacrylamide is 400 × 104~3000 × 104。
Preferably, nonionic surfactant accounts for 0.04%~0.3%, and cationic oligo surfactant accounts for 0.05%
~1.5%, high molecular polymer accounts for 0.04%~0.3%, and surplus is water.
The emulsifying and viscosity-reducing agent for condensed oil the preparation method comprises the following steps: nonionic surfactant, cationic oligomeric surface is living
Property agent and high molecular polymer completely dissolve in water (for dissolution concrete mode without particular/special requirement, this field can be used
The thinkable various modes of technical staff institute) to get.
Further, the preparation method comprises the following steps: under mechanical agitation, high molecular polymer is added in the water of part, stirring
To abundant dissolution, nonionic surfactant and cationic oligo surfactant is then added, the water of surplus is added, stirs
To being completely dissolved.
Emulsifying and viscosity-reducing agent for condensed oil of the invention can be effectively reduced the viscosity of high-content wax viscous crude, and salt-resistance is good, to containing
The viscous crude of the water flooding of high calcium and magnesium ion has good adaptability；Dosage it is low (be used for reducing thick oil viscosity when, thinner
Dosage is 20% or more of viscous crude, preferably 20%~70%), it is low using concentration, it is at low cost, without adding alkali to use, can be applicable in
In the quick stratum of alkali.
In the present invention, stirring generally refers to the stirring under 200~400rpm revolving speed.Part water is generally the 1/ of water inventory
3~2/3.The abundant dissolution conditions of high molecular polymer are as follows: generally at normal temperature, such as at 15~30 DEG C, stir 3~5 hours；Add
It stirs after entering other components to the condition being completely dissolved are as follows: generally at normal temperature, such as at 15~30 DEG C, stir 20~30min.
All documents recited in the present invention, their full content are incorporated herein by reference, and if these are literary
When offering expressed meaning and the inconsistent present invention, it is subject to statement of the invention.In addition, the various terms that use of the present invention and
Phrase is with well known to a person skilled in the art general senses.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.However, the scope of the present invention is not limited to following realities
Apply example.One of skill in the art, can be to the present invention it is understood that under the premise of without departing substantially from the spirit and scope of the present invention
Carry out various change and modification.
Instrument involved in following embodiments, reagent, material etc. are unless otherwise noted existing in the prior art
Conventional instrument, reagent, material etc., can be obtained by regular commercial sources.Experimental method involved in following embodiments, inspection
Survey method etc. is unless otherwise noted existing routine experiment method in the prior art, detection method etc..
Embodiment prepares emulsifying pour depressor
Room temperature (15~30 DEG C), 200~400rpm revolving speed mechanical agitation under, by high molecular polymer be added to
Water is in the water of total amount 1/3~2/3, and stirring is sufficiently dissolved for 3~5 hours to polymer；Then non-ionic surface active is added
The water of surplus is added in agent and cationic oligo surfactant, stirs 20~30min to being completely dissolved, and is configured to emulsification drop
Stick.
(the single-stranded surfactant of cationic substitutes cationic oligo surfactant, no for each embodiment and comparative example
Add cationic oligo surfactant or high molecular polymer, or both do not add) in emulsifying pour depressor composition be shown in Table
1, wherein R is straight chained alkyl.
The composition of emulsifying pour depressor in 1 embodiment of table and comparative example
The test of test case thick-oil emulsified adhesive-reducing
Test oil chooses two kinds of high-content wax viscous crude.Viscous crude A is Zhongyuan Oil Field content of wax viscous crude (50 DEG C of viscosity
98000mPa.s, wax content 13%, wax content is measured according to SY/T0537-2008 in crude oil)；Viscous crude B is the Jiangsu oilfield content of wax
Viscous crude (50 DEG C of viscosity 9630mPa.s, wax content 25%).Viscosity reduction process are as follows: in beaker, take above-described embodiment of certain mass
Or the emulsifying pour depressor in comparative example, it is added in the test oil of certain mass, beaker is placed in constant temperature in 50 DEG C of water-baths
2h stirs 10min, observes emulsified viscous oil form, then measures viscosity at 50 DEG C.
In order to test the salt-resistance of emulsifying pour depressor, when carrying out viscous crude B reducing viscosity by emulsifying performance test, thinner preparation method
In wet concentration select mineralized water, salinity 160000mg/L, wherein Ca2+Concentration are as follows: 10000mg/L, Mg2+Concentration are as follows:
10000mg/L；And when carrying out viscous crude A reducing viscosity by emulsifying performance test, the wet concentration in thinner preparation method selects deionized water, mineralising
Degree is 0mg/L, wherein Ca2+Concentration are as follows: 0mg/L, Mg2+Concentration are as follows: 0mg/L.
In this test case, for the ease of comparison, the emulsifying pour depressor dosage that viscosity reduction test is chosen is unified for the 30% of viscous crude,
By weight.
The measurement of medium viscosity of the present invention: Brookfield DV-II viscosimeter is used at 50 DEG C, is in shear rate
7.34s-1Under conditions of be measured.Measurement result is as shown in table 2.
2 embodiment of table and comparative example viscosity reduction test result
Examples 1 to 4 and embodiment 5,6 are compared as can be seen that on the basis of the weight of emulsifying pour depressor, it is non-from
The content of sub- surfactant is 0.04%~0.3%, the content of cationic oligo surfactant be 0.05%~
1.5%, when content 0.04%~0.3% of high molecular polymer, reduce the better effect of viscosity of thickened oil.
Examples 1 to 6 is compared with embodiment 7 as can be seen that the R in cationic oligo surfactant is
C8-C16When alkyl chain length, the better effect of viscosity of thickened oil is reduced.
By embodiment 1 with comparative example 1 be compared as can be seen that cationic oligo surfactant compared with cationic
Single-stranded surfactant can significantly reduce viscosity of thickened oil at higher concentration (0.1%).But in low concentration condition
Under (0.05% or less), embodiment 6 and comparative example 2, when reaching identical viscosity reducing effect, oligo surfactant viscosity reduction system makes
It is lower with concentration.
Embodiment 1 and comparative example 3~5 are compared as can be seen that cationic oligo surfactant and macromolecule
Polymer is indispensable in emulsifying pour depressor of the present invention, and otherwise viscous crude does not emulsify.That is: high-content wax viscous crude and high calcium-containing magnesium are directed to
Water flooding condition, nonionic surfactant, cationic oligo surfactant and high molecular polymer component are indispensable.
Above-described embodiment is provided to those skilled in the art, how to implement and use to be advocated with full disclosure and description
Embodiment, rather than for limiting range disclosed herein.Obvious modification will to those skilled in the art
Within the scope of the appended claims.
Claims (10)
1. a kind of emulsifying and viscosity-reducing agent for condensed oil, it is characterised in that: by nonionic surfactant, cationic oligomeric surface activity
Agent, high molecular polymer and water composition, wherein nonionic surfactant accounts for 0.01%~1%, and cationic oligomeric surface is living
Property agent accounts for 0.02%~3%, and high molecular polymer accounts for 0.01%~1%, and surplus is water, by weight；
The nonionic surface active agent is selected from alkylphenol-polyethenoxy base ether and/or alkylol polyoxyethylene base ether；
The cationic oligo surfactant is selected from one or more of compound A, compound B, compound C；
The compound A, compound B, compound C structural formula respectively as shown in (a) (b) (c) in formula (I)；In formula (I), R is
C4~C18Alkyl；X is selected from F-、Cl-、Br-、I-One or more of；
(a)
(b)
(c)
The high molecular polymer is in polyacrylamide, xanthan gum, hydroxypropyl guar, carboxymethyl cellulose, polyvinyl alcohol
One or more.
2. emulsifying and viscosity-reducing agent for condensed oil according to claim 1, it is characterised in that: the alkylphenol-polyethenoxy base ether and/
Or the degree of polymerization of alkylol polyoxyethylene base ether is 3~30, alkyl chain length is 6~20.
3. emulsifying and viscosity-reducing agent for condensed oil according to claim 2, it is characterised in that: the alkylphenol-polyethenoxy base ether is selected from
Nonylphenol polyoxyethylene ether series NP-7, NP-10, NP-15；The alkylol polyoxyethylene base ether is selected from aliphatic alcohol polyethenoxy
Ether series A EO-7, AEO-9, AEO-13.
4. emulsifying and viscosity-reducing agent for condensed oil according to claim 1, it is characterised in that: the viscosity average molecular weigh of the polyacrylamide
It is 400 × 104~3000 × 104。
5. emulsifying and viscosity-reducing agent for condensed oil according to claim 1, it is characterised in that: the emulsifying and viscosity-reducing agent for condensed oil is by with the following group
Be grouped as: nonionic surfactant accounts for 0.04%~0.3%, and cationic oligo surfactant accounts for 0.05%~1.5%,
High molecular polymer accounts for 0.04%~0.3%, and surplus is water.
6. emulsifying and viscosity-reducing agent for condensed oil according to any one of claims 1 to 5, it is characterised in that: the emulsified viscous oil drop
Stick is selected from following one:
1. composed of the following components: nonylphenol polyoxyethylene ether NP-10 accounts for 0.05%, and cationic oligo surfactant accounts for
0.1%, the polyacrylamide that viscosity average molecular weigh is 10,000,000 accounts for 0.1%, and surplus is water；Wherein, cationic oligomeric surface is living
Property agent structural formula such as in formula (I) shown in (a), R C12Alkyl, X Br-；
2. composed of the following components: nonylphenol polyoxyethylene ether NP-7 accounts for 0.3%, and cationic oligo surfactant accounts for
0.8%, the polyacrylamide that viscosity average molecular weigh is 4,000,000 accounts for 0.3%, and surplus is water；Wherein, cationic oligomeric surface activity
In the structural formula such as formula (I) of agent shown in (b), R C14Alkyl, X Br-；
3. composed of the following components: fatty alcohol polyoxyethylene ether AEO-9 accounts for 0.1%, and cationic oligo surfactant accounts for
0.05%, the polyacrylamide that viscosity average molecular weigh is 30,000,000 accounts for 0.04%, and surplus is water；Wherein, cationic oligomeric surface
In the structural formula such as formula (I) of activating agent shown in (c), R C10Alkyl, X Br-；
4. composed of the following components: fatty alcohol polyoxyethylene ether AEO-13 accounts for 0.04%, and cationic oligo surfactant accounts for
1.5%, hydroxypropyl guar accounts for 0.2%, and surplus is water；Wherein, in the structural formula of cationic oligo surfactant such as formula (I)
(a) shown in, R C8Alkyl, X Cl-。
7. emulsifying and viscosity-reducing agent for condensed oil according to any one of claims 1 to 5, it is characterised in that: the emulsified viscous oil drop
Stick is selected from following one:
5. composed of the following components: nonylphenol polyoxyethylene ether NP-10 accounts for 0.01%, and cationic oligo surfactant accounts for
0.1%, the polyacrylamide that viscosity average molecular weigh is 10,000,000 accounts for 0.1%, and surplus is water；Wherein, cationic oligomeric surface is living
Property agent structural formula such as in formula (I) shown in (a), R C10Alkyl, X Br-；
6. composed of the following components: nonylphenol polyoxyethylene ether NP-10 accounts for 0.05%, and cationic oligo surfactant accounts for
0.02%, the polyacrylamide that viscosity average molecular weigh is 10,000,000 accounts for 0.01%, and surplus is water；Wherein, cationic oligomeric surface
In the structural formula such as formula (I) of activating agent shown in (c), R C10Alkyl, X Br-；
7. composed of the following components: nonylphenol polyoxyethylene ether NP-10 accounts for 0.05%, and cationic oligo surfactant accounts for
0.1%, the polyacrylamide that viscosity average molecular weigh is 10,000,000 accounts for 0.1%, and surplus is water；Wherein, cationic oligomeric surface is living
Property agent structural formula such as in formula (I) shown in (a), R C18Alkyl, X F-。
8. the preparation method of emulsifying and viscosity-reducing agent for condensed oil according to any one of claims 1 to 7, it is characterised in that: by nonionic
Surfactant, cationic oligo surfactant and high molecular polymer completely dissolve in water to get.
9. the preparation method of emulsifying and viscosity-reducing agent for condensed oil according to claim 8, it is characterised in that: in mechanical agitation
Under, high molecular polymer is added in the water of part, then nonionic surfactant and cation is added to abundant dissolution in stirring
Type oligo surfactant, is added the water of surplus, and stirring is to being completely dissolved.
10. application of the emulsifying and viscosity-reducing agent for condensed oil according to any one of claims 1 to 7 in the viscosity for reducing content of wax viscous crude.
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| CN112680293A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Emulsifier, preparation method and application thereof, and method for emulsifying butter in alkaline washing tower |
| CN113930230A (en) * | 2021-12-16 | 2022-01-14 | 中海油田服务股份有限公司 | Thick oil viscosity reducer and preparation method thereof |
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| CN112680293A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Emulsifier, preparation method and application thereof, and method for emulsifying butter in alkaline washing tower |
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| CN113930230A (en) * | 2021-12-16 | 2022-01-14 | 中海油田服务股份有限公司 | Thick oil viscosity reducer and preparation method thereof |
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| CN109111906B (en) | 2020-10-13 |
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