CN109420364A - Demulsifier and preparation method thereof and demulsification method for hydrocarbon oil - Google Patents
Demulsifier and preparation method thereof and demulsification method for hydrocarbon oil Download PDFInfo
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- CN109420364A CN109420364A CN201710765837.9A CN201710765837A CN109420364A CN 109420364 A CN109420364 A CN 109420364A CN 201710765837 A CN201710765837 A CN 201710765837A CN 109420364 A CN109420364 A CN 109420364A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
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- C—CHEMISTRY; METALLURGY
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
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- C—CHEMISTRY; METALLURGY
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of demulsifiers and preparation method thereof, and the invention also discloses the demulsification method for hydrocarbon oil using the demulsifier.The demulsifier contains at least one Formulas I compound represented.Demulsifier according to the present invention has good demulsification to hydrocarbon ils, particularly acid-containing raw oil, can obtain higher dehydration efficiency, and the oil content that can be effectively reduced in the water of abjection.
Description
Technical field
The present invention relates to a kind of demulsifiers, prepare the invention further relates to a kind of preparation method of demulsifier and by this method
Demulsifier, the invention further relates to a kind of demulsification method for hydrocarbon oil.
Background technique
Crude oil demulsification dehydration is a key link for guaranteeing that oil gas proper set is defeated, nowadays the land most crude oils in China
For composite water cut up to 80% or more, many crude oil Produced Liquids are aqueous more than 90%, and even up to 95% or more, if too late
When be dehydrated, will increase pump, pipeline and basin load, cause corrosion and fouling；And it discharges the oil contained in water and also can
Environmental pollution and crude oil is caused to waste.Therefore, either economically, or from environmental protection angle, be both needed to crude oil into
Row breaking emulsion and dewatering.The advantages that active high, quick due to chemical demulsifier, adding demulsifier is most common demulsification
Method.
Crude oil in China component is complex, different geographical, different blocks, the oil of even different oil wells there is also difference,
And demulsifier has stronger specific aim, this just increases the research and development difficulty of demulsifier.The most commonly used demulsification in China at present
Agent is the propylene oxide of different structure, epoxyethane block copolymer, and majority is two, three block structure.According to the literature, China
Independent development production, the demulsifier kind applied are more than 200 kinds, only demulsification of the Shandong BinHua Group Co., Ltd in production
Agent is just more than 70 kinds.
With the development of China Petroleum, the implementation of especially various intensified oil reduction measures, the ingredient of Produced Liquid is more
Complexity, breaking emulsion and dewatering difficulty increase, it is necessary to which development of new high-efficient demulsifier is especially used for the demulsification of ternary combination flooding produced liquid
Agent.
Summary of the invention
The purpose of the present invention is to provide a kind of novel crude oil demulsifier, which has good demulsification to hydrocarbon ils
Effect especially has good demulsification to crude oil.
According to the first aspect of the invention, the present invention provides a kind of demulsifier, which contains at least one Formulas I
Compound represented:
In Formulas I, R1、R2、R3And R4It is identical or different, respectively hydrogen,Or
And R1、R2、R3And R4At least one of beR7For-(OR9)m, m R9It is identical or different, respectively
C2-C8Alkylidene, m is a numerical value within the scope of 1-1000, R6And R8It is identical or different, respectively hydrogen or C1-C5's
Alkyl, R18For C1-C5Alkyl, n is a numerical value within the scope of 1-400；
The hydroxyl value of the demulsifier is 10-70mg/g.
According to the second aspect of the invention, the present invention provides a kind of preparation method of demulsifier, this method include with
Lower step:
(1) under the conditions of Michael addition reaction, in the presence of at least one alcohol, by polyetheramine shown in formula IV and extremely
Acrylate contact shown in a kind of few Formula V, and the alcohol in the mixture that contact obtains is removed, obtain product of contact, formula IV institute
The molar ratio of acrylate shown in the polyetheramine and Formula V shown is 1:3-4,
In formula IV, R5For hydrogen or C1-C5Alkyl, n is a numerical value within the scope of 1-400,
In Formula V, R18For hydrogen or C1-C5Alkyl, R19For C1-C5Alkyl；
(2) under transesterification conditions, the product of contact that step (1) obtains is contacted with polyethers shown in Formula IV, it is described to connect
The molar ratio for touching polyethers described in the total amount and Formula IV of ester group in product is 1:0.25-1,
H-(OR9)m- OH (Formula IV)
In Formula IV, m R9It is identical or different, respectively C2-C8Alkylidene, m is a number within the scope of 1-1000
Value.
According to the third aspect of the present invention, the present invention provides a kind of method systems as described in the second aspect of the present invention
Standby demulsifier.
According to the fourth aspect of the present invention, the present invention provides a kind of demulsification method for hydrocarbon oil, this method includes by hydrocarbon ils
It is mixed with demulsifier, obtained mixture is subjected to water-oil separating, obtain water phase and oily phase, wherein the demulsifier is this hair
Demulsifier described in terms of bright first aspect or third.
Demulsifier according to the present invention especially has good demulsification to crude oil (such as acid-containing raw oil) to hydrocarbon ils,
Higher dehydration efficiency, and the oil content that can be effectively reduced in the water of abjection can be obtained.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
According to the first aspect of the invention, the present invention provides a kind of demulsifier, which contains at least one Formulas I
Compound represented:
In Formulas I, R1、R2、R3And R4It is identical or different, respectively hydrogen,Or
And R1、R2、R3And R4At least one of beSuch as R1、R2、R3And R4In any one, any two,
Any three or any four areFrom the angle for the demulsification for further increasing demulsifier,
R1、R2、R3And R4In at least three beIt is highly preferred that R1、R2、R3And R4It is
In Formulas I, R7For-(OR9)m, m R9It is identical or different, respectively C2-C8Alkylidene, specific example can wrap
Include but be not limited to ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, sub- sec-butyl, isobutylidene, sub- tert-butyl, Asia positive penta
Base, isoamylidene, sub- tertiary pentyl, sub- neopentyl, sub- n-hexyl, sub- n-heptyl or sub- n-octyl.Preferably, m R9It is identical
Or it is different, respectivelyM indicates the degree of polymerization, can be one within the scope of 1-1000
Numerical value, a numerical value preferably within the scope of 5-500, a numerical value more preferably within the scope of 10-200.From further
The angle for improving the demulsification of demulsifier is set out, and m is a numerical value within the scope of 25-100, such as within the scope of 27-75
One numerical value.In the present invention, " within the scope of x-y " includes two endpoint values, that is, includes x and y.
In Formulas I, R6And R8It is identical or different, respectively hydrogen or C1-C5Alkyl.Specifically.R6And R8Respectively can be
Hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, 2- methyl butyl, 3- first
Base butyl or 2,2- dimethyl propyl.Preferably, R6And R8Respectively C1-C5Alkyl.It is highly preferred that R6And R8Respectively first
Base.
In Formulas I, R18For C1-C5Alkyl.Specifically, R18Can for methyl, ethyl, n-propyl, isopropyl, normal-butyl,
Sec-butyl, isobutyl group, tert-butyl, n-pentyl, 2- methyl butyl, 3- methyl butyl or 2,2- dimethyl propyl.Preferably, R18
For methyl.
In Formulas I, n indicates the degree of polymerization, can be a numerical value within the scope of 1-400, preferably within the scope of 2-200
One numerical value, a numerical value more preferably within the scope of 3-100, a numerical value further preferably within the scope of 3-50,
It is still more preferably a numerical value within the scope of 3-20, a numerical value particularly preferably within the scope of 3-10, such as in 3-5
A numerical value in range.
Demulsifier described in first aspect according to the present invention, the hydroxyl value of the demulsifier are 10-70mg/g, preferably 15-
60mg/g, more preferably 20-40mg/g.In the present invention, hydroxyl value is using phthalic anhydride method specified in GB/T7383-1997
Measurement, wherein hydroxyl value is defined as neutralizing with the hydroxyl in phthalic anhydride esterification 1g sample and the required KOH of the acid that generates
Milligram number, can also simply be defined as the KOH milligram number of hydroxyl in 1g sample, unit mg/g.
Demulsifier described in first aspect according to the present invention, in one embodiment, in demulsifier shown in Formulas I,
R1、R2、R3And R4It isAccording to the demulsifier of the embodiment, hydroxyl value is preferably 25-60mg/g, more
Preferably 30-40mg/g.
Demulsifier described in first aspect according to the present invention, in another embodiment, demulsifier shown in Formulas I
In, R1、R2、R3And R4In any three beRemaining as hydrogen orAccording to this
The demulsifier of embodiment, hydroxyl value are preferably 15-40mg/g, more preferably 20-30mg/g.
According to the second aspect of the invention, the present invention provides a kind of preparation method of demulsifier, this method includes step
Suddenly (1): under the conditions of Michael addition reaction, in the presence of at least one alcohol, by polyetheramine shown in formula IV and at least one
Acrylate contact shown in kind Formula V, and the alcohol in the mixture that contact obtains is removed, product of contact is obtained,
In formula IV, R5For hydrogen or C1-C5Alkyl.Specifically, in formula IV, R5It can be hydrogen, methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, 2- methyl butyl, 3- methyl butyl or 2,2- bis-
Methyl-propyl.
In formula IV, n can be for a numerical value within the scope of 1-400, a numerical value preferably within the scope of 2-200,
A numerical value more preferably within the scope of 3-100, a numerical value further preferably within the scope of 3-50 are further excellent
It is selected as a numerical value within the scope of 3-20, a numerical value particularly preferably within the scope of 3-10, one such as within the scope of 3-5
A numerical value.
Method described in the second aspect according to the present invention, polyetheramine shown in formula IV are specifically as follows polyetheramine D230.
In Formula V, R18For hydrogen or C1-C5Alkyl, specific example can include but is not limited to hydrogen, methyl, ethyl, just
Propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, 2- methyl butyl, 3- methyl butyl or 2,2-
Dimethyl propyl.Preferably, R18For methyl.
In Formula V, R19For C1-C5Alkyl, specific example can include but is not limited to methyl, ethyl, n-propyl, isopropyl
Base, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, 2- methyl butyl, 3- methyl butyl or 2,2- dimethyl propylene
Base.Preferably, R19For methyl.
Acrylate shown in Formula V is specifically as follows but is not limited to methyl acrylate, methyl methacrylate, acrylic acid second
Ester, ethyl methacrylate, butyl acrylate or butyl methacrylate.Preferably, acrylate shown in Formula V is third
E pioic acid methyl ester and/or methyl methacrylate.Preferably, acrylate shown in Formula V is methyl acrylate and/or metering system
Sour methyl esters.
In step (1), the molar ratio of acrylate shown in polyetheramine shown in formula IV and Formula V is 1:3-4.
In step (1), in the presence of at least one alcohol, by acrylate shown in polyetheramine shown in formula IV and Formula V
On the one hand contact, the alcohol can be used as the solvent of reaction, on the other hand plays the role of catalyst.The alcohol is preferably C1-C5
Aliphatic alcohol, specific example can include but is not limited to methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, uncle
The combination of one or more of butanol, n-amyl alcohol, 2- methyl butanol.Preferably, the alcohol is methanol.
The dosage of the alcohol can be selected according to the dosage of polyetheramine and acrylate.Generally, the alcohol and formula
The molar ratio of acrylate shown in II can be 1-8:1, preferably 2-4:1.
In step (1), polyetheramine shown in formula IV is contacted with acrylate shown in Formula V carries out Michael addition reaction,
So that with the amino in polyetheramine molecular structure addition reaction occurs for the unsaturated double-bond in acrylate molecule structure.It can be
It is sufficient to make polyetheramine and acrylate to occur to be reacted under conditions of Michael addition reaction.Generally, in step (1),
Can by acrylate shown in polyetheramine shown in formula IV and Formula V 10-50 DEG C, preferably 20-40 DEG C, it is 25-35 DEG C more preferable
At a temperature of contacted.The duration of the contact can be selected according to the temperature of contact.Generally, the contact
Duration can be 1-36 hours, preferably 5-24 hours.
Method described in the second aspect according to the present invention in step (1), can be obtained using conventional method removing contact
Mixture in alcohol, to obtain product of contact.As an example, can be contacted by the method removing that solvent evaporates
To mixture in alcohol.
Method described in the second aspect according to the present invention, including step (2): under transesterification conditions, step (1) is obtained
To product of contact contacted with polyethers shown in Formula IV,
H-(OR9)m- OH (Formula IV).
In Formula IV, m R9It is identical or different, respectively C2-C8Alkylidene, specific example can include but is not limited to
Ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, sub- sec-butyl, isobutylidene, sub- tert-butyl, sub- n-pentyl, sub- isoamyl
Base, sub- tertiary pentyl, sub- neopentyl, sub- n-hexyl, sub- n-heptyl or sub- n-octyl.Preferably, m R9It is identical or different, respectively
From for M indicates the degree of polymerization, can be a numerical value within the scope of 1-1000, preferably
A numerical value for a numerical value within the scope of 5-500, more preferably within the scope of 10-200.From further increasing preparation
The angle of the demulsification of demulsifier is set out, and m is a numerical value within the scope of 25-100, and one such as within the scope of 27-75
Numerical value.
Method described in the second aspect according to the present invention, in step (2), the ester in product of contact that step (1) obtains
Base is (that is,-COOR19) with Formula IV shown in polyethers occur ester exchange reaction.The dosage of polyethers shown in Formula IV can be according to expection
Ester exchange reaction degree selected.Generally, polyethers shown in the total amount and Formula IV of ester group rubs in the product of contact
Your ratio can be 1:0.25-1.From the angle for the demulsification ability for further increasing the demulsifier finally prepared, the contact
The molar ratio of polyethers shown in the total amount and Formula IV of ester group is preferably 1:0.75-1 in product, more preferably 1:1.The contact produces
The total amount of ester group can be determined using nuclear magnetic resonance spectroscopy in object, can also be determined according to the inventory of step (1).
It, can the generation ester friendship of the polyethers described in the product of contact and Formula IV for being sufficient to make step (1) to obtain in step (2)
It changes under conditions of reacting and carries out.It generally, can be by polyethers shown in product of contact and Formula IV that step (1) obtains in 40-200
It is contacted at a temperature of DEG C.Preferably, polyethers shown in the product of contact and Formula IV step (1) obtained 90-160 DEG C,
It is preferred that 95-140 DEG C, it is 100-120 DEG C more preferable at a temperature of contacted.The duration of the contact can be according to contact
Temperature is selected.Generally, the duration of the contact can be 1-20 hours, preferably 4-10 hours.
In step (2), the contact is preferably carried out in the presence of at least one catalyst.The catalyst can be pair
Ester exchange reaction has the substance of catalytic action, can be acid or alkali.As a preferred embodiment, the catalyst is alkali.
Preferably, the catalyst is alkali metal hydroxide.It is highly preferred that the catalyst is sodium hydroxide and/or potassium hydroxide.
The dosage of the catalyst can be catalytic amount.Generally, the molar ratio of the catalyst and polyethers can be 0.001-1:1,
Preferably 0.01-0.8:1.
Method described in the second aspect according to the present invention, in step (2), from the degree for further increasing ester exchange reaction
Angle set out, during contact, will reaction generate small molecular alcohol (i.e.-R19OH reaction system) is discharged.It can use
The small molecular alcohol generated in conventional method removing ester-exchange reaction, such as: it can be by the way of inert gas purge, it will
The small molecular alcohol generated in ester-exchange reaction takes reaction system out of, and the inert gas, which refers to, is not involved in ester exchange reaction
Gaseous matter, specific example can include but is not limited to: the combination of one or more of nitrogen, argon gas and helium.
Method described in the second aspect according to the present invention, step (2) obtains mixture can make directly as demulsifier
With.
According to the third aspect of the present invention, the present invention provides a kind of method systems as described in the second aspect of the present invention
Standby demulsifier.
According to the present invention in terms of first aspect and third described in demulsifier, have for aqueous hydrocarbon ils good broken
Newborn ability can effectively remove the water in aqueous hydrocarbon ils lotion, and not only water speed is fast out, but also dehydrating amount is high, obtained dehydration
The water content of hydrocarbon ils is low.
According to the fourth aspect of the present invention, the present invention provides a kind of demulsification method for hydrocarbon oil, this method includes by hydrocarbon ils
It is mixed with demulsifier, obtained mixture is subjected to water-oil separating, obtain water phase and oily phase, wherein the demulsifier is this hair
Demulsifier described in terms of bright first aspect or third.The demulsifier and its composition and preparation method are above
It is described in detail, and will not be described here in detail.
Breaking method described in 4th aspect according to the present invention, the hydrocarbon ils can be the hydrocarbon ils in various sources.One
In kind preferred embodiment, the hydrocarbon ils is crude oil, preferably acid-containing raw oil.The acid value of the acid-containing raw oil (in terms of KOH)
It can be 0.6-8mg/g, preferably 2-6mg/g.The acid value is using potentiometric titration side specified in GB/T 18609-2011
Method measurement.
Breaking method described in 4th aspect according to the present invention, the dosage of the demulsifier can be conventional selection.One
As, the additive amount of the demulsifier can be 20-300mg/L, preferably 50-260mg/L.4th aspect according to the present invention
The demulsifier that the breaking method uses has good demulsification ability, even if also can effectively break under lower dosage
Oil removing aqueous emulsion.Preferably, the additive amount of the demulsifier is 100-200mg/L.
Breaking method described in 4th aspect according to the present invention, can under normal conditions mix demulsifier and hydrocarbon ils
It closes, and carries out water-oil separating.Generally, can 100 DEG C -140 DEG C, preferably 110-120 DEG C at a temperature of, by hydrocarbon ils and demulsification
Agent mixing.The mixture of hydrocarbon ils and demulsifier can be carried out by water-oil separating using conventional method, such as: settle and separate.According to
Breaking method described in the 4th aspect of the present invention, hydrocarbon ils can also be mixed with demulsifier in the presence of an electric field and carry out oil
Water separation.
The present invention will be described in detail with EXPERIMENTAL EXAMPLE with reference to embodiments, but the range being not intended to limit the present invention.
Embodiment 1-7 is for illustrating demulsifier and preparation method thereof of the invention.
In following embodiment and comparative example, the hydroxyl value of demulsifier is using phthalic acid specified in GB/T7383-1997
Acid anhydride method measurement, wherein hydroxyl value is defined as needed for neutralizing the acid generated with the hydroxyl in phthalic anhydride esterification 1g sample
KOH milligram number, can also simply be defined as the KOH milligram number of hydroxyl in 1g sample, unit mg/g.
Embodiment 1
(1) 230g (1.0mol) polyetheramine D230 (is purchased from Huntsman Chemistry company, molecular formula isR5For methyl, average molecular weight 230) and 500g anhydrous methanol be added to stirring
In the three-necked flask of device and nitrogen protection device, it is uniformly mixed.Then, constant pressure is added in 345g (4.0mol) methyl acrylate
It titrates in funnel, is added drop-wise in three-necked flask, reacted for 24 hours with stirring in room temperature (for 25 DEG C).After reaction, it will react
To mixture be evaporated that (wherein, Rotary Evaporators are heated using water-bath, bath temperature 40 with Rotary Evaporators
DEG C), methanol is removed, product is obtained.
The product is characterized using Fourier transform infrared spectrometry, determines that in wave number be 2950cm-1、2850cm-1、1720cm-1、1410cm-1、1180cm-1And 1120cm-1There is stronger absorption peak at place, in 1640cm-1Locate not apparent
Absorption peak (absorption peak corresponds to the double bond in methyl acrylate), shows without methyl acrylate in product, while in 3500-
3300cm-1Place also without there is apparent absorption peak (N-H that the absorption peak corresponds to primary amine), shows in product without primary amine groups
Group.
(2) 57.5g (is determined, the content of ester group is 0.4mol in product) that step (1) is obtained by the feed ratio of step (1)
Product, 600g (0.4mol) polyether polyol (molecular formula be H- (OR9)m- OH, R9For ethylidene, average molecular weight is
1500) and 2.5g sodium hydroxide is added in the three-necked flask with mechanical stirring and nitrogen protection device, in nitrogen protection
Under, the temperature of reaction solution is increased to 100 DEG C with stirring, and reacted at such a temperature, separated during the reaction anti-
The methanol that should be generated stops reaction, obtains demulsifier according to the present invention, the demulsifier until separating there is no methanol
Hydroxyl value be 32.14mg/g.
The demulsifier is characterized using Fourier transform infrared spectrometry, determines that in wave number be 3460cm-1、
1950cm-1、1930cm-1、1640cm-1、1440cm-1、1370cm-1、1110cm-1And 1010cm-1There is stronger absorption at place
Peak.
Embodiment 2
Demulsifier is prepared using method same as Example 1, unlike, in step (2), the polyether polyol of use
Average molecular weight be 600, to obtain demulsifier according to the present invention, the hydroxyl value of the demulsifier is 58.62mg/g.
Embodiment 3
Demulsifier is prepared using method same as Example 1, unlike, in step (2), the polyether polyol of use
Average molecular weight be 1000, to obtain demulsifier according to the present invention, the hydroxyl value of the demulsifier is 45.31mg/g.
Embodiment 4
Demulsifier is prepared using method same as Example 1, unlike, in step (2), the polyether polyol of use
Average molecular weight be 1200, the hydroxyl value of the demulsifier is 39.26mg/g.
Comparative example 1
Demulsifier is prepared using method same as Example 1, unlike, in step (1) polyetheramine D230 with etc. rub
The ethylenediamine of your amount replaces, to obtain demulsifier, the hydroxyl value of the demulsifier is 46.25mg/g.
Comparative example 2
Demulsifier is prepared using method same as Example 1, unlike, in step (1) polyetheramine D230 with etc. rub
The hexamethylene diamine of your amount replaces, to obtain demulsifier, the hydroxyl value of the demulsifier is
Embodiment 5
(1) 230g (1.0mol)) polyetheramine (is purchased from Huntsman Chemistry company, molecular formula isR5For hydrogen, average molecular weight 230) and 400g methanol be added to agitating device and
In the three-necked flask of nitrogen protection device, it is uniformly mixed.Then, constant pressure drop is added in 345g (4.0mol) methyl methacrylate
Determine in funnel, be added drop-wise in three-necked flask, reacts 5h in room temperature (for 30 DEG C) with stirring.After reaction, reaction is obtained
Mixture be evaporated that (wherein, Rotary Evaporators are heated using water-bath, bath temperature 40 with Rotary Evaporators
DEG C), methanol is removed, product is obtained.
The product is characterized using Fourier transform infrared spectrometry, is determined in 1640cm-1Locate no apparent absorption peak
(absorption peak corresponds to the double bond in methyl methacrylate) shows without methyl methacrylate in product, while
3500-3300cm-1Place also without there is apparent absorption peak (N-H that the absorption peak corresponds to primary amine), shows to be free of in product
Primary amine group.
(2) 57.5g (is determined, the content of ester group is 0.4mol in product) that step (1) is obtained by the feed ratio of step (1)
Product, 1530g (0.3mol) polyether polyol (molecular formula be H- (OR9)m- OH, R9ForMean molecule
Amount is 5100) and 0.1g sodium hydroxide is added in the three-necked flask with mechanical stirring and nitrogen protection device, protects in nitrogen
Under shield, the temperature of reaction solution is increased to 100 DEG C with stirring, and reacted at such a temperature, separated during the reaction
The methanol generated is reacted, until being separated there is no methanol, stops reaction, obtains demulsifier according to the present invention, the demulsification
The hydroxyl value of agent is 26.14mg/g.
Embodiment 6
Demulsifier is prepared using method same as Example 5, unlike, the dosage of polyether polyol in step (2)
For 0.4mol, to obtain demulsifier according to the present invention, the hydroxyl value of the demulsifier is 22.35mg/g.
Embodiment 7
Demulsifier is prepared using method same as Example 5, unlike, in step (1), polyetheramine and metering system
The molar ratio of sour methyl esters is 1:3, and the dosage of polyether polyol is same as Example 5 in step (2), to obtain according to the present invention
Demulsifier, the hydroxyl value of the demulsifier is 30.38mg/g.
EXPERIMENTAL EXAMPLE 1-14 is for illustrating breaking method according to the present invention.
EXPERIMENTAL EXAMPLE 1-14
In following EXPERIMENTAL EXAMPLE, using in GB/T8929 " detecting crude oil water content method --- the way of distillation " measurement crude oil
Water content, using the dewatering of SY/T5281-2000 " demulsifier service performance detection method --- bottle tries method " measurement demulsifier.
EXPERIMENTAL EXAMPLE 1-7
For the crude oil used for Peng Lai acid-containing raw oil, the acid value of the acid-containing raw oil is 3.28mg/g, and water content is 0.5 weight
Measure %, wherein using the acid value of the measurement crude oil of constant-current titration method specified in GB/T 18609-2011.
EXPERIMENTAL EXAMPLE 1-7 110 DEG C at a temperature of demulsifier prepared by embodiment 1-7 is mixed with acid-containing raw oil respectively
It closes, wherein the additive amount of demulsifier is 200mg/L, and the method according to specified in SY/T5281-2000 carries out dewatering survey
Examination calculates the water yield under different time, and observes the water quality and oil-water interfaces of water outlet, as a result lists in table 1.
Experimental comparison's example 1-2
Using the dewatering of the demulsifier of method identical with EXPERIMENTAL EXAMPLE 1-7 measurement comparative example 1-2 preparation, as a result
It is listed in table 1.
Experimental comparison's example 3
Polyetheramine D230 using method identical with EXPERIMENTAL EXAMPLE 1-7 measurement as the raw material of 1 step of embodiment (1)
Dewatering, as a result listed in table 1.
Experimental comparison's example 4
The dewatering for the product that 1 step of embodiment (1) obtains is measured using method identical with EXPERIMENTAL EXAMPLE 1-7,
As a result it is listed in table 1.
Experimental comparison's example 5
Polyether polyol using method identical with EXPERIMENTAL EXAMPLE 1-7 measurement as the raw material of 1 step of embodiment (2)
Dewatering, as a result listed in table 1.
Experimental comparison's example 6
Demulsifier is not added, is as a result listed in table 1.
Table 1
EXPERIMENTAL EXAMPLE 1-7's as a result, it was confirmed that demulsifier according to the present invention is shown in the breaking emulsion and dewatering of acid-containing raw oil
Good demulsification performance out can effectively remove the water in acid-containing raw oil, and the water quality of the water separated is clear, shows therein
Oil content is low.
EXPERIMENTAL EXAMPLE 8-14
EXPERIMENTAL EXAMPLE 8-14 110 DEG C at a temperature of demulsifier prepared by embodiment 1-7 and triumph are managed into defeated original respectively
Oil mixing, wherein the additive amount of demulsifier is 100mg/L, and the method according to specified in SY/T5281-2000 carries out dehydration property
It can test, calculate the water yield under different time, and observe the water quality and oil-water interfaces of water outlet, as a result listed in table 2.
Experimental comparison's example 7-8
Using the dewatering of the demulsifier of method identical with EXPERIMENTAL EXAMPLE 8-14 measurement comparative example 1-2 preparation, knot
Fruit is listed in table 2.
Experimental comparison's example 9
Polyetheramine using method identical with EXPERIMENTAL EXAMPLE 8-14 measurement as the raw material of 1 step of embodiment (1)
As a result the dewatering of D230 is listed in table 2.
Experimental comparison's example 10
The dewatering for the product that 1 step of embodiment (1) obtains is measured using method identical with EXPERIMENTAL EXAMPLE 8-14,
As a result it is listed in table 2.
Experimental comparison's example 11
Polyether polyols using method identical with EXPERIMENTAL EXAMPLE 8-14 measurement as the raw material of 1 step of embodiment (2)
As a result the dewatering of alcohol is listed in table 2.
Experimental comparison's example 12
Demulsifier is not added, is as a result listed in table 2.
Table 2
EXPERIMENTAL EXAMPLE 8-14's as a result, it was confirmed that demulsifier according to the present invention shows good demulsification performance, can have
Water in effect ground removing hydrocarbon ils, and the water quality of the water separated is clear, shows that oil content therein is low.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (21)
1. a kind of demulsifier, which contains at least one Formulas I compound represented:
In Formulas I, R1、R2、R3And R4It is identical or different, respectively hydrogen,OrAnd
R1、R2、R3And R4At least one of beR7For-(OR9)m, m R9It is identical or different, respectively C2-
C8Alkylidene, m is a numerical value within the scope of 1-1000, R6And R8It is identical or different, respectively hydrogen or C1-C5Alkane
Base, R18For C1-C5Alkyl, n is a numerical value within the scope of 1-400；
The hydroxyl value of the demulsifier is 10-70mg/g.
2. demulsifier according to claim 1, wherein in demulsifier shown in Formulas I, R1、R2、R3And R4It isThe hydroxyl value of the demulsifier is preferably 25-60mg/g, more preferably 30-40mg/g.
3. demulsifier according to claim 1, wherein in demulsifier shown in Formulas I, R1、R2、R3And R4In any three
ForRemaining as hydrogen orThe hydroxyl value of the demulsifier is preferably 15-40mg/g, more
Preferably 20-30mg/g.
4. demulsifier described in any one of -3 according to claim 1, wherein m R9It is identical or different, respectively
5. demulsifier described in any one of -4 according to claim 1, wherein m is a numerical value within the scope of 5-500,
A numerical value preferably within the scope of 10-200, a numerical value more preferably within the scope of 25-100.
6. demulsifier described in any one of -5 according to claim 1, wherein R5For methyl.
7. demulsifier described in any one of -6 according to claim 1, wherein n is a numerical value within the scope of 2-200,
A numerical value preferably within the scope of 3-100, a numerical value more preferably within the scope of 3-50, further preferably in 3-
A numerical value in 20 ranges is still more preferably a numerical value within the scope of 3-10.
8. a kind of preparation method of demulsifier, method includes the following steps:
(1) under the conditions of Michael addition reaction, in the presence of at least one alcohol, by polyetheramine shown in formula IV and at least one
The contact of acrylate shown in kind of Formula V, and remove the alcohol in the mixture that contact obtains, obtains product of contact, shown in formula IV
The molar ratio of acrylate shown in polyetheramine and Formula V is 1:3-4,
In formula IV, R5For hydrogen or C1-C5Alkyl, n is a numerical value within the scope of 1-400,
In Formula V, R18For hydrogen or C1-C5Alkyl, R19For C1-C5Alkyl；
(2) under transesterification conditions, the product of contact that step (1) obtains is contacted with polyethers shown in Formula IV, the contact produces
The molar ratio of polyethers shown in the total amount and Formula IV of ester group is 1:0.25-1 in object,
H-(OR9)m- OH (Formula IV)
In Formula IV, m R9It is identical or different, respectively C2-C8Alkylidene, m is a numerical value within the scope of 1-1000.
9. according to the method described in claim 8, wherein, R5For methyl.
10. method according to claim 8 or claim 9, wherein n is a numerical value within the scope of 2-200, preferably in 3-
A numerical value in 100 ranges, a numerical value more preferably within the scope of 3-50, further preferably within the scope of 3-20
One numerical value is still more preferably a numerical value within the scope of 3-10.
11. the method according to any one of claim 8-10, wherein in step (1), the contact is at 10-50 DEG C
At a temperature of carry out, the duration of the contact is preferably 1-36 hours.
12. the method according to any one of claim 8-11, wherein the alcohol is methanol, ethyl alcohol, propyl alcohol, butanol
One or more of with hexanol.
13. the method according to any one of claim 8-12, wherein acrylate shown in the alcohol and Formula II
Molar ratio is 1-8:1.
14. the method according to any one of claim 8-13, wherein m R9It is identical or different, respectively
15. the method according to any one of claim 8-14, wherein m is a numerical value within the scope of 5-500,
A numerical value preferably within the scope of 10-200, a numerical value more preferably within the scope of 25-100.
16. the method according to any one of claim 8-15, wherein in step (2), ester group in the product of contact
Total amount and Formula IV described in polyethers molar ratio be 1:0.75-1.
17. the method according to any one of claim 8-16, wherein in step (2), the contact is at 40-200 DEG C
At a temperature of carry out, preferably 90-160 DEG C at a temperature of carry out, the duration of the contact is preferably 1-20 hours, more excellent
It is selected as 4-10 hours.
18. a kind of demulsifier of the preparation of the method as described in any one of claim 8-17.
19. a kind of demulsification method for hydrocarbon oil, this method includes mixing hydrocarbon ils with demulsifier, and obtained mixture is carried out grease point
From obtaining water phase and oily phase, which is characterized in that the demulsifier is demulsification described in any one of claim 1-7 and 18
Agent.
20. breaking method according to claim 19, wherein the additive amount of the demulsifier is 20-200mg/L, preferably
For 100-200mg/L.
21. breaking method described in 9 or 20 according to claim 1, wherein the hydrocarbon ils is crude oil, preferably acid-containing raw oil, institute
The acid value for stating acid-containing raw oil is preferably 0.6-8mgKOH/g.
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| US5661220A (en) * | 1993-08-10 | 1997-08-26 | Basf Aktiengesellschaft | Reaction products of olefinically unsaturated carboxylic acids and polyetherols and their use as demulsifiers for crude oil emulsions |
| US20110082061A1 (en) * | 2009-10-02 | 2011-04-07 | Exxonmobil Research And Engineering Company | Alkylated naphtylene base stock lubricant formulations |
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