CN106221728B - A kind of preparation method of polyelectrolyte type crude oil desalting demulsifier - Google Patents
A kind of preparation method of polyelectrolyte type crude oil desalting demulsifier Download PDFInfo
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- CN106221728B CN106221728B CN201610644945.6A CN201610644945A CN106221728B CN 106221728 B CN106221728 B CN 106221728B CN 201610644945 A CN201610644945 A CN 201610644945A CN 106221728 B CN106221728 B CN 106221728B
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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
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The present invention relates to a kind of preparation method of polyelectrolyte type crude oil desalting demulsifier.Comprise the following steps that：(1) by the amination modified of poly glycol monomethyl ether；(2) glycidyl dimethyl alkyl ammomium chloride is prepared；(3) quaternized carboxyalkyl chitosan is prepared；(4) modified poly (ethylene glycol) monomethyl ether and quaternized carboxyalkyl chitosan reaction, obtain target product poly glycol monomethyl ether and be grafted quaternized carboxyalkyl chitosan.The present invention has many advantages, such as wide material sources, natural, nontoxic, sustainable, product bio-compatibility is good, degradable using chitosan class natural polymer as raw material.Not only breaking emulsion and dewatering effect is good for the demulsifier being prepared, simultaneously because contain substantial amounts of carboxyalkyl group and quaternary ammonium salt group on demulsification agent molecule, there is very strong binding ability in electronegative particle to the electronegative ions such as metal cation, cycloalkanes acid group and surface, therefore have the ability of removing oil-soluble salt concurrently while demulsification.
Description
Technical field
The present invention relates to a kind of preparation method of polyelectrolyte type crude oil desalting demulsifier, belong to petrochemical industry.
Background technology
With developing rapidly for industry, the demand of oil is increasing, and raising oil recovery has very important
Meaning.Because the usage amount of chemical flooding constantly increases, the heaviness of crude oil and peracid value getting worse in addition, the gold in crude oil
Category ion concentration is gradually increasing.Salt in crude oil is mainly inorganic salts, is mostly dissolved in the water contained by it, and water forms surely with oil
Fixed Water-In-Oil (W/O) type emulsion.The key of crude oil desalting is to be dehydrated, and the key being dehydrated is to be demulsified.In crude oil
Natural emulsion absorption has the viscoplasticity film of some strength in oil-water interfaces, formation, and dynamics barrier is caused to emulsion droplet coalescence
Hinder, crude oil emulsion is provided with stability.The principle of demulsification is to destroy the factor of emulsion stabilization, both at home and abroad to crude oil demulsification
Study and more successfully develop many breaking methods.Oil field most commonly adds demulsifier, and demulsifier is current oil field and refining
One of essential chemical reagent of factory.With the development of petroleum industry, the demand of demulsifier increasingly increases, will to its performance
Ask also more harsh.If developing a kind of new and effective advanced desalination demulsifier, can be removed while demulsification oily molten
Property salt, will to crude oil in China process be of great significance.
The method of crude oil demulsification mainly has chemical method, electrical method, centrifugal separation, supercritical ultrasonics technology, bioanalysis etc..It is wherein chemical
Method and electrical method are the most frequently used, but electrical method requires higher to equipment and process conditions, implement more complicated, early investment and later stage operation
Expense is all higher；Chemical method is a kind of method of economical rationality.
The demulsification process of demulsifier is generally divided into 3 stages：(1) after demulsifier adds crude oil emulsion, it is allowed to be dispersed in
In whole oil phase, and it can enter in the globule being emulsified；(2) demulsifier penetrates into the protective layer of the emulsification globule, and makes protective layer
Fragile crumple destroys, and after protecting damage layer, the globule being emulsified is close to each other and contacts；(3) globule coalesces, the globule being emulsified
From continuously to separating.
From 1914 report Barnickel with 0.1% FeS04Solution makes emulsification crude oil demulsification at 35 DEG C~60 DEG C
Rise, successively develop three generations's demulsifier.The 1920s to the thirties to solve the demulsification of oil-in-water type crude oil emulsion, occurs
First generation low molecule ionic demulsifying agent, such as soap, naphthenate anionic demulsifier, quaternaries cation
Type demulsifier.This type demulsifier advantage is cheap, and shortcoming is that dosage is big, effect is poor, easily influenceed by electrolyte.20
The forties in century to the fifties, the industrialization of ethylene oxide production have promoted going out for ethylene oxide propylene oxide block copolymer
It is existing.Thus the demulsifier of second generation Water-In-Oil emulsified crude oil, mainly low molecule nonionic surface active agent have been developed.From 20
After the sixties in century, people develop demulsifier of the third generation based on high relative molecular mass polyethers.Foreign countries break to crude oil
Emulsion has carried out substantial amounts of research, it is proposed that substantial amounts of patent.The nonionic surfactant as demulsifier is with alkane earliest
Base phenol, fatty alcohol are prepared as hydrophobic group, a number of oxirane of graft copolymerization.It is big with tertiary oil recovery technology
Scale on-site is tested, and novel crude oil demulsifier continues to bring out.Into after the eighties, simple oxirane propylene oxide block polyethers
Demulsifier starts to be substituted by polyamine class, polymer-type, amphoteric ion type demulsifier, and minimum amount drops to below 100mg/L.But
The shortcomings that these demulsifiers is that selectivity is strong, bad adaptability.Therefore people further through modified or building preparation composite demulsifying agent with
And super high molecular weight high-efficient demulsifier, so as to which the application study of demulsifier has been pushed to a new step.
To solve the above problems, occurs the method that more initiators prepare crude oil demulsifier in recent years.Chinese patent
CN200510130345 describes a kind of polyether-type crude oil demulsifier.Using polyethylene polyamine or nonylphenolic resin as initiator,
React to obtain polyethers with oxirane, expoxy propane, then polyethers and chain extender, pyridine hybrid reaction are obtained.The invention has system
Standby technique is simple, and dosage is few, and breaking emulsion and dewatering effect is good, low cost and other advantages, but the demulsifier can not reach low-temperature demulsification to save
Save the effect of heat energy.Chinese patent CN 201410710742 describes a kind of low temperature crude oil demulsifier.With Glycidyl methacrylate
Glyceride, Hexafluorobutyl mathacrylate are that initiator and acetone, acrylic acid copolymer obtain.Evade needed for existing product demulsification
Temperature is high, demulsification time length, the drawbacks of being dehydrated water quality inferiority.It can at low temperature be demulsified, reduce ton oil consumption tolerance, save the energy, carry
High economic benefit and equipment treatment effeciency.But the demulsifier selectivity is strong, less stable, it is impossible to is adapted to a variety of different types of
Crude oil demulsification.Chinese patent CN 201310289037.6 describes a kind of polysaccharide-modified crude oil demulsifier.Using polysaccharide as starting
Agent, and it is carried out it is quaternised modified, it is polyether graft modified, the demulsifier have wide material sources, it is natural, nontoxic, sustainable, make
With security it is good many advantages, such as.Not only breaking emulsion and dewatering effect is good for the demulsifier, and be demulsified great amount of hydroxy group contained in agent molecule etc.
Group has certain chelant ability to metal ion, but binding ability is not strong, it is impossible to dehydration while deviate from variety classes and
Substantial amounts of metal cation, also need to be improved.Therefore, it is necessary to develop a kind of low-temperature demulsification, fast emulsion breaking, demulsifier pair is expanded
The crude oil scope of application and the demulsifier for having good dewatering and desalting effect concurrently.
Chitin wide material sources, content are only second to cellulose, are the organic compound of the second in the world major class.Chitosan is first
The product of shell element deacetylation, compared with xanthans and guar gum, containing the amino that reactivity is bigger on strand, it is more easy to
Graft modification.Chitosan class natural polymer has fabulous biocompatibility and environment friendly, and molecular weight is big, active hydrogen
Rheologic behavio(u)r more, that there is branched structure and uniqueness.Its derivative has stronger flocculation ability, occupied by oil-water interfaces
Area it is big, have preferable temperature tolerance, higher interfacial activity, be demulsifier initiator splendid candidate target.Shell gathers
Carboxyalkyl and quaternary ammonium salt group are introduced into sugar subchain to be had very to the electronegative ion such as metal cation, cycloalkanes acid group in crude oil
Strong binding ability.Simultaneously by controlling position and the substitution value of each substituent, and polyether lateral chain, carboxyalkyl group and quaternary ammonium
The length of segment on salt groups, a series of high-efficient demulsifiers for being appropriate to heterogeneity crude oil are can obtain, and can be in demulsification
Slough oil-soluble salt simultaneously.
The content of the invention
The purpose of the present invention is to propose a kind of polyelectrolyte type crude oil for above-mentioned problems of the prior art and take off
The preparation method of salt demulsifier, obtain it is a series of be appropriate to heterogeneity crude oil, and oil-soluble can be sloughed while demulsification
The high-efficient demulsifier of salt.
To achieve the above object, technical scheme provided by the invention is as follows：
A kind of preparation method of polyelectrolyte type crude oil desalting demulsifier, it is characterised in that comprise the following steps：
1) poly glycol monomethyl ether terminal hydroxy group progress amination is obtained into amination modified poly glycol monomethyl ether；
2) preparation of glycidyl dimethyl alkyl ammomium chloride：To N, epoxy chloropropionate is added dropwise in N- dimethyl alkylamines
Alkane, 25 DEG C~40 DEG C are warming up to, 6~30h of isothermal reaction, reaction product is isolated and purified, obtains glycidyl dimethyl alkane
Ammonium chloride；Wherein described N, the carbon chain lengths of alkyl are C in N- dimethyl alkylamines6‐C34；
3) preparation of quaternized carboxyalkyl chitosan：Carboxyalkyl chitosan is dissolved using solvent orange 2 A, adjusted using alkali lye molten
Liquid pH value, then reaction system is added dropwise to after the glycidyl dimethyl alkyl ammomium chloride obtained by step 2) is dissolved in into solvent orange 2 A,
60~80 DEG C are warming up to, after reacting 8~24h, reaction solution is dialysed, is freeze-dried, obtains the quaternized carboxyalkyl shell of solid product
Glycan；
4) modified poly (ethylene glycol) monomethyl ether and quaternized carboxyalkyl chitosan reaction：Quaternized carboxylic alkane prepared by step 3)
Base enclosure glycan is dissolved in solvent B, is stirred continuously at room temperature, adds a certain amount of catalyst, prepared by step 1) amination modified
Poly glycol monomethyl ether is added drop-wise in reaction system after being dissolved in solvent B, reacts at room temperature 24~48h, and reaction solution is dialysed 3~5 days,
Liquid Residue is freeze-dried to produce target product crude oil demulsifier-poly glycol monomethyl ether and be grafted quaternized carboxyalkyl shell and gathered in bag
Sugar.
In such scheme, it is preferable that step 1) is described amination modified to be concretely comprised the following steps：By 1 molar part polyethylene glycol
Monomethyl ether is dissolved in solvent C, keeps reaction 1~2 molar part catalyst to be added, by 2.5~5 moles in inert gas environment
Part sulfonylation agent is slowly dropped in reaction solution after being dissolved in solvent C, 0 DEG C of 3~5h of reaction of ice-water bath, it is molten to be evaporated under reduced pressure removing
Agent, solvent D recrystallizations are added, recrystallized product is added in 10~20 molar part amination reagents, 140~160 DEG C of backflows
6~8h is reacted, is evaporated under reduced pressure, freeze-drying obtains amination poly glycol monomethyl ether；Wherein, the poly glycol monomethyl ether
The equal molecular mass of number is 350,500,750,1000,1900 or 5000.Preferably, the solvent C is dichloromethane, chloroform, four
One or more in chlorination carbon, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide.Preferably, the solvent D is second
Ether, the one or more in isopropyl ether, methyl tertiary butyl ether(MTBE).Preferably, the catalyst is pyridine or triethylamine.Preferably,
The sulfonylation agent is paratoluensulfonyl chloride.Preferably, the amination reagent is ammoniacal liquor.Preferably, the inert gas
Environment is nitrogen or argon gas.
By such scheme, it is preferable that in step 2), the N, the mass fraction of N- dimethyl alkylamines and epoxychloropropane
Than for 1.93~2.97：3.7.
By such scheme, it is preferable that described to isolate and purify to be dried in vacuo after being eluted with acetone in step 2).
By such scheme, it is preferable that the preparation method of the carboxyalkyl chitosan described in step 3) is：
By weight, 1.61 parts of chitosans are swelled, alkali lye regulation suspension are used as alkalescence, in -15 DEG C~-25 DEG C bars
Be stirred overnight under part, add 7.4~14.8 parts of carboxylated reagent chloro alkyl acid sodium, be warming up to 30~60 DEG C of stirring reactions 3~
12h, reaction product is isolated and purified, freeze-drying obtains carboxyalkyl chitosan；Wherein, the carbon chain length of the chloro alkyl acid sodium
Spend for C2-C10.Preferably, it is described to isolate and purify specially：Filtering, by obtained solid product 80% ethanol and absolute ethyl alcohol
It is drying for one day in 60 DEG C after rinsing respectively, then dialysed after solid is dissolved in into water.
By such scheme, it is preferable that in step 3), described carboxyalkyl chitosan and glycidyl dimethyl alkyl chloride
The quality parts ratio for changing ammonium is 3.21：1.93~7.7.
By such scheme, it is preferable that in step 3), described pH value range is 8~10.
By such scheme, it is preferable that in step 3), carboxyalkyl chitosan is being dissolved using solvent orange 2 A and is using alkali lye to adjust
After saving solution ph, then the solution is warming up to 45~50 DEG C, isothermal reaction 1h.The effect of this step is to allow carboxyalkyl chitosan
Chain is fully opened, and grafting is more uniform.
By such scheme, it is preferable that in step 4), the quaternized carboxyalkyl chitosan, catalyst, the poly- second two of amination
The quality parts ratio of alcohol monomethyl ether is 0.47~1.05:0.115~0.206:1.75~25.
By such scheme, it is preferable that in step 4), the catalyst includes but is not limited to carbodiimides, dicyclohexyl
Carbodiimide, n-hydroxysuccinimide.
By such scheme, it is preferable that described solvent orange 2 A is distilled water, isopropanol, sodium hydroxide solution, hydrochloric acid solution, N,
N-dimethylformamide, N, one or more mixing in N dimethyl acetamide, dimethyl sulfoxide, acetic acid, methanol.
By such scheme, it is preferable that the solvent B is distilled water, isopropanol, sodium hydroxide solution, N, N- dimethyl methyls
One or more in acid amides, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, acetic acid, methanol.
By such scheme, it is preferable that in each step, the alkali lye is sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid
One or more in potassium.
The synthetic route of the present invention is as follows：
1st, poly glycol monomethyl ether is modified：
2nd, prepared by glycidyl dimethyl alkyl ammomium chloride：
R2=CH2(CH2)qCH3Q=4,6,8,10,12,14,16....32
3rd, chitosan carboxylation alkylation is modified, and quaternised modified product reacts with modified poly (ethylene glycol) monomethyl ether：
R=H or COCH3 R1=H or (CH2)pCOONa p=1,2,3,4,5.6,7,8,9
R2=CH2(CH2)qCH3Q=0,2,4,6,8,10,12,14,16....32
R3=H or R1 or(CH2)pCO-NH-MPEG a+b+c=m
In the prior art, traditional polyether type demulsifying agent is generally using oxirane, expoxy propane as primary raw material, selection tool
The material for having active hydrogen is initiator, and block polymer demulsifier is obtained by polymerizeing etherificate；As oilfield exploitation enters the later stage, greatly
Quantify compound drive largely to use in recovery process, this process exacerbates emulsification of crude oil degree, the difficulty of increase demulsification, and block gathers
The demulsification performance of ether demulsifier is limited.The present invention compared with prior art, has the advantages that：
1) present invention has wide material sources, natural, nontoxic, biological using chitosan class natural polymer as raw material
Degradability and it is compatible, sustainable, safety in utilization is good many advantages, such as.
2) obtained by poly glycol monomethyl ether, chlorine alkyl acid sodium, the modification of glycidyl dimethyl alkyl ammomium chloride
Chitin modified demulsifier there is molecular weight height, highly branched chain, pectinate texture, carboxyalkyl and dimethyl alkyl ammomium chloride in side chain
There is very strong binding ability in electronegative particle to the electronegative ion such as metal cation and cycloalkanes acid group and surface, therefore
The chitin modified natural polymer demulsifier of the present invention has good dewatering and desalting effect；
3) in the present invention, when preparing carboxyalkyl chitosan, by the method for low temperature alkalization, hydrogen in chitosan molecule can be made
Key is easier to be opened, and alkali lye is easier to penetrate into chitosan molecule, and then carboxyalkyl side chain is more uniformly grafted to shell and gathered
On sugar backbone, thus obtained carboxyalkyl chitosan structure is stable and dissolution properties are good.
4) method that chitosan class natural macromolecule modification crude oil desalting demulsifier is prepared in the present invention, can be by selecting not
With the carboxyalkyl acid sodium of carbon chain lengths, N, N- dimethyl alkylamines, polyethers, either change reaction raw materials amount ratio or change
The condition such as the reaction temperature of reaction system and time, so as to change demulsifier molecular structure such as molecular weight, substitution value, hydrophobic segment
Length aggregated structure etc., and then regulate and control the desalting and dewatering effect of the high-efficient demulsifier of synthesis, with (different suitable for heterogeneity
The place of production, saliferous water content are different) crude oil.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content be not limited solely to following example.
Embodiment 1
A kind of preparation of polyelectrolyte type crude oil desalting demulsifier, comprises the following steps：
(1) poly glycol monomethyl ether terminal hydroxy group is amination modified：Taking polyethylene glycol monomethyl ether (Mn=350) 1.75g
(5mmol) is dissolved in 10mL dichloromethane, keeps reaction to add 0.69mL (5mmol) triethylamine in ar gas environment, will
2.38g (12.5mmol) paratoluensulfonyl chloride, which is dissolved in dichloromethane, to be slowly dropped in reaction solution, (0 DEG C) reaction of ice-water bath
3h.It is evaporated under reduced pressure, adds 100mL Diethyl ether recrystallization, recrystallized product is added in 3.85mL (0.1mol) ammoniacal liquor, added
Heat is to 140 DEG C of back flow reaction 6h.It is evaporated under reduced pressure, freeze-drying obtains amino-polyethyleneglycols monomethyl ether；
(2) prepared by glycidyl dimethyl lauryl ammonium chloride：To equipped with agitator, dropping funel and condensing reflux
2.13g Dodecyl Dimethyl Amines are added in the three-necked flask of device, is stirred continuously, takes 3.7g epoxychloropropane to pass through dropping liquid
Funnel is added dropwise to complete in 30min, 25 DEG C of keeping temperature, isothermal reaction 6h.Stop reaction, product is eluted with acetone, and vacuum is done
It is dry, obtain glycidyl dimethyl lauryl ammonium chloride.
(3) preparation of carboxymethyl chitosan：1.61g chitosans are added in 250mL flask, add 10mL isopropanols
Swelling, 2.5mL 10mol/L sodium hydroxide solution is added, continue to stir 30min, be stirred overnight under the conditions of -15 DEG C, added
7.4g sodium chloroacetates, rear heating response mixed liquor is added completely to 60 DEG C and continues stirring reaction 3h.Filtered after the completion of reaction anti-
Mixture is answered to obtain crude product, product is washed 3 times respectively with 80% ethanol and absolute ethyl alcohol, is put into 60 DEG C of drying box and is dried
After one day, solid is dissolved in water and dialysed 3 days, is freeze-dried to obtain CMC；
(4) preparation of quaternized carboxymethyl chitosan：3.21g CMCs are weighed in three-necked flask, are added
Enter 40mL distilled water, adjust pH=8~10 with sodium hydroxide solution, be warming up to 50 DEG C, isothermal reaction 1h；2.78g is shunk sweet
Oil base lauryl ammonium chloride is dissolved in 20mL water to be added drop-wise in reaction system by constant pressure funnel, is heated up 80 DEG C, reacts 8h.Instead
After the completion of answering, reaction solution is dialysed 4 days, freeze-drying obtains the quaternized carboxymethyl chitosan of solid product；
(5) modified poly (ethylene glycol) monomethyl ether reacts with quaternized carboxymethyl chitosan：Take the quaternized carboxymethyl chitosans of 0.47g
Sugar is placed in 250mL three-necked flasks, is added the dissolving of 30mL water, is stirred at room temperature, adds 0.115g n-hydroxysuccinimides,
1.75g aminations poly glycol monomethyl ether (Mn=350) is dissolved in 10mL water, is added dropwise to complete in 10min, reacts 30h.With saturating
Analyse bag to dialyse 3 days, Liquid Residue is freeze-dried the quaternized carboxymethyl for producing target product-poly glycol monomethyl ether grafting in bag
Chitosan, it is demulsifier 1.
Embodiment 2
A kind of preparation of polyelectrolyte type crude oil desalting demulsifier, comprises the following steps：
(1) poly glycol monomethyl ether terminal hydroxy group is amination modified：Taking polyethylene glycol monomethyl ether (Mn=750) 3.75g
(5mmol) is dissolved in 10mL dichloromethane, keeps reaction to add 1.38mL (10mmol) triethylamine in ar gas environment, will
4.76g (25mmol) paratoluensulfonyl chloride, which is dissolved in dichloromethane, to be slowly dropped in reaction solution, (0 DEG C) reaction 4h of ice-water bath.
It is evaporated under reduced pressure, adds 100mL Diethyl ether recrystallization, recrystallized product is added in 3.85mL (0.1mol) ammoniacal liquor, heats
To 140 DEG C of back flow reaction 7h.It is evaporated under reduced pressure, freeze-drying obtains amino-polyethyleneglycols monomethyl ether；
(2) prepared by glycidyl dimethyl tetradecyl ammonium chloride：To equipped with agitator, dropping funel and condensing reflux
2.41g dodecyldimethylamine base tertiary amines are added in the three-necked flask of device, is stirred continuously, takes 3.7g epoxychloropropane to pass through dropping liquid
Funnel is added dropwise to complete in 30min, 30 DEG C of keeping temperature, isothermal reaction 20h.Stop reaction, product is eluted with acetone, and vacuum is done
It is dry, obtain glycidyl dimethyl tetradecyl ammonium chloride.
(3) preparation of carboxyetbyl chitosan：1.61g chitosans are added in 250mL flask, add 10mL isopropanols
Swelling, 2.5mL 10mol/L sodium hydroxide solution is added, continue to stir 30min, be stirred overnight under the conditions of -20 DEG C, added
8.2g chloropropionic acid sodium, rear heating response mixed liquor is added completely to 60 DEG C and continues stirring reaction 4h.Filtered after the completion of reaction anti-
Mixture is answered to obtain solid product, product is washed 3 times respectively with 80% ethanol and absolute ethyl alcohol, is put into 60 DEG C of drying box and is done
It is dry, then dialysed 5 days after solid is dissolved in into water, it is freeze-dried to obtain solid product N, O- carboxyetbyl chitosan.
(4) preparation of quaternized carboxyetbyl chitosan：3.21g N are weighed, O- carboxyetbyl chitosans add in three-necked flask
Enter 40mL distilled water, adjust pH=8~10 with sodium hydroxide solution, be warming up to 45 DEG C, isothermal reaction 1h.2.78g is shunk sweet
Oil base tetradecyl ammonium chloride is dissolved in 20mL water to be added drop-wise in reaction system by constant pressure funnel, is warming up to 70 DEG C, reaction
16h.After the completion of reaction, reaction solution is dialysed 5 days, and freeze-drying obtains the quaternized carboxyetbyl chitosan of solid product.
(5) modified poly (ethylene glycol) monomethyl ether reacts with quaternized carboxyetbyl chitosan：The quaternized carboxyethyl shells of 0.53g are taken to gather
Sugar is placed in 250mL three-necked flasks, is added the dissolving of 30mL dimethyl sulfoxides, is stirred at room temperature, adds 0.191g carbodiimides, will
In 3.75g aminations poly glycol monomethyl ether (Mn=750) 10mL dimethyl sulfoxides, it is added dropwise to complete in 10min, reacts 30h.With saturating
Analyse bag to dialyse 3 days, Liquid Residue is freeze-dried the quaternized carboxyethyl for producing target product-poly glycol monomethyl ether grafting in bag
Chitosan, it is demulsifier 2.
Embodiment 3
A kind of preparation of polyelectrolyte type crude oil desalting demulsifier, comprises the following steps：
(1) poly glycol monomethyl ether terminal hydroxy group is amination modified：Taking polyethylene glycol monomethyl ether (Mn=1000) 5g
(5mmol) is dissolved in 10mL dichloromethane, keeps reaction to add 1.38mL (10mmol) triethylamine in ar gas environment, will
4.76g (25mmol) paratoluensulfonyl chloride, which is dissolved in dichloromethane, to be slowly dropped in reaction solution, (0 DEG C) reaction 5h of ice-water bath.
It is evaporated under reduced pressure, adds 100mL Diethyl ether recrystallization, recrystallized product is added in 3.85mL (0.1mol) ammoniacal liquor, heats
To 140 DEG C of back flow reaction 8h.It is evaporated under reduced pressure, freeze-drying obtains amino-polyethyleneglycols monomethyl ether；
(2) prepared by glycidyl dimethyl cetyl chloride ammonium：To equipped with agitator, dropping funel and condensing reflux
2.69g hexadecyldimethyl benzyl ammonium tertiary amines are added in the three-necked flask of device, is stirred continuously, is taken 3.7g epoxychloropropane and use dropping liquid
Funnel is added dropwise to complete in 30min, 40 DEG C of keeping temperature, after isothermal reaction 30h, stops reaction.Product is washed with acetone, vacuum
Dry, obtain glycidyl dimethyl cetyl chloride ammonium.
(3) preparation of carboxylic propyl group chitosan：1.61g chitosans are added in 250mL flask, add 10mL isopropanols
Swelling, 2.5mL 10mol/L sodium hydroxide solution is added, continue to stir 30min, be stirred overnight under the conditions of -25 DEG C, added
9.5g chloro-butyric acid sodium, rear heating response mixed liquor is added completely to 30 DEG C and continues stirring reaction 12h.Filtered after the completion of reaction anti-
Mixture is answered to obtain solid product, product is washed 3 times respectively with 80% ethanol and absolute ethyl alcohol, is put into 60 DEG C of drying box and is done
It is dry, then dialysed 4 days after solid is dissolved in into water, it is freeze-dried to obtain solid product N, O- carboxylic propyl group chitosan.
(4) preparation of quaternized carboxylic propyl group chitosan：3.21g N are weighed, O- carboxylic propyl group chitosans add in three-necked flask
Enter 40mL distilled water, adjust pH=8~10 with sodium hydroxide solution, be warming up to 45 DEG C, isothermal reaction 1h.2.86g is shunk sweet
Oleyl dimethyl cetyl chloride ammonium is dissolved in 20mL water to be added drop-wise in reaction system by constant pressure funnel, is warming up to 60 DEG C,
React 24h.After the completion of reaction, reaction solution is dialysed 5 days, and freeze-drying obtains the quaternized carboxylic propyl group chitosan of solid product.
(5) modified poly (ethylene glycol) monomethyl ether and quaternized carboxylic propyl group chitosan reaction：The quaternized carboxylic propyl group shells of 0.64g are taken to gather
Sugar is placed in 250mL three-necked flasks, is added the dissolving of 30mL DMFs, is stirred at room temperature, adds the rings of 0.206g bis-
Hexyl carbodiimide, 5g aminations poly glycol monomethyl ether (Mn=1000) is dissolved in 10mL DMFs,
It is added dropwise to complete in 10min, reacts 40h.Dialysed 4 days with bag filter, Liquid Residue, which is freeze-dried, in bag produces target product-poly- second
The quaternized carboxylic propyl group chitosan of glycol monomethyl ether grafting, is demulsifier 3.
Embodiment 4
A kind of preparation of polyelectrolyte type crude oil desalting demulsifier, comprises the following steps：
(1) poly glycol monomethyl ether terminal hydroxy group is amination modified：Taking polyethylene glycol monomethyl ether (Mn=5000) 5g
(1mmol) is dissolved in 10mL dichloromethane, keeps reaction to add 0.3mL (2mmol) triethylamine in ar gas environment, will
0.95g (5mmol) paratoluensulfonyl chloride, which is dissolved in dichloromethane, to be slowly dropped in reaction solution, (0 DEG C) reaction 5h of ice-water bath.Subtract
Pressure distillation, adds 100mL Diethyl ether recrystallization, recrystallized product is added in 1mL (0.02mol) ammoniacal liquor, is heated to 140
DEG C back flow reaction 8h.It is evaporated under reduced pressure, freeze-drying obtains amino-polyethyleneglycols monomethyl ether；
(2) prepared by glycidyl dimethyl dotriacontane ammonium chloride：To equipped with agitator, dropping funel and condense back
Flow and 2.97g dotriacontyl dimethyl tertiary amines are added in the three-necked flask of device, be stirred continuously, take 3.7g epoxychloropropane to pass through
Dropping funel is added dropwise to complete in 30min, 40 DEG C of keeping temperature, isothermal reaction 30h.Stop reaction, product is eluted with acetone, very
Sky is dried, and obtains glycidyl dimethyl dotriacontane ammonium chloride.
(3) preparation of carboxylic nonyl chitosan：1.61g chitosans are added in 250mL flask, add 10mL isopropanols
Swelling, 2.5mL 10mol/L sodium hydroxide solution is added, continue to stir 30min, be stirred overnight under the conditions of -20 DEG C, added
14.8g chlorine sodium caprates, rear heating response mixed liquor is added completely to 60 DEG C and continues stirring reaction 3h.Filtered after the completion of reaction anti-
Mixture is answered to obtain crude product, product is washed 3 times respectively with 80% ethanol and absolute ethyl alcohol, is put into 60 DEG C of drying box and is dried
After one day, solid is dissolved in water and dialysed 3 days, is freeze-dried to obtain N, O- carboxylic nonyl chitosans；
(4) preparation of quaternized carboxylic nonyl chitosan：3.21g CMCs are weighed in three-necked flask, are added
Enter 40mL dimethyl sulfoxides, adjust pH=8~10 with sodium hydroxide solution, be warming up to 50 DEG C, isothermal reaction 1h；7.7g is shunk sweet
Oil base dotriacontane ammonium chloride is dissolved in 20mL dimethyl sulfoxides, is added drop-wise to by constant pressure funnel in reaction system, is heated up 80 DEG C,
React 8h.After the completion of reaction, reaction solution is dialysed 3 days, freeze-drying obtains the quaternized carboxylic nonyl chitosan of solid product；
(5) modified poly (ethylene glycol) monomethyl ether and quaternized carboxylic nonyl chitosan reaction：The quaternized carboxylic nonyl shells of 1.05g are taken to gather
Sugar is placed in 250mL three-necked flasks, is added the dissolving of 30mL water, is stirred at room temperature, 0.191g carbodiimides is added, by 25g ammonia
Base polyethylene glycol monomethyl ether (Mn=5000) is dissolved in 10mL water, is added dropwise to complete in 10min, reacts 40h.Dialysed with bag filter
5 days, Liquid Residue was freeze-dried the quaternized carboxylic nonyl chitosan for producing target product-poly glycol monomethyl ether grafting in bag, is
Demulsifier 4.
Comparative example 1
Quaternized carboxymethyl chitosan made from step (4) is as demulsifier comparative example 1 in Example 1.
Comparative example 2
It is a kind of poly- according to made from the method for embodiment 1 in Chinese patent application CN201310289037.6 bulletin text
Electrolyte type crude oil desalting demulsifier is as demulsifier comparative example 2.
Comparative example 3
Using commercially available product designation JL series demulsifier as demulsifier comparative example 3
Demulsifying effect of demulsifier is tested
Present invention demulsification experiment oil is used as using the crude oil that Wuhan Branch, Sinopec Corp. provides
Tested, be measured by GB/T 8929-88 (way of distillation), it is 50% to measure water content in crude oil.
Dehydration temperaturre is set as 60~80 DEG C, demulsifier concentration is 70~120ppm in crude oil.With reference to Chinese people's republicanism
State oil and gas industry standard SY/T 5281-2000《Crude oil demulsifier performance detection method (bottle examination method)》, it is right respectively
Demulsifier comparative example 1-3 demulsification performance is tested made from demulsifier 1-4 made from embodiment 1-4 and comparative example,
The concussion method of dehydration test bottle uses mechanical concussion method in experiment.
Comprise the following steps that：Crude oil emulsion sample is poured into 100mL tool plug graduated cylinders, water bath with thermostatic control heating 30min；With
Pipette is filled in graduated cylinder to tool adds a certain amount of crude oil demulsification agent solution；Using mechanical concussion method, amplitude is more than 20cm, concussion
Time is 5min, and after fully mixing, tool plug graduated cylinder is replaced in into standing sedimentation in water bath with thermostatic control；Start timing, record is different
The dehydrating amount of time (5min, 15min, 30min, 60min, 120min), when terminating sedimentation, observational record sewage color and profit
State of interface.
Experimental result is shown, compared to demulsifier comparative example 1-3, according to the demulsifier 1-4 that the inventive method obtains de-
Coolant-temperature gage is 60~80 DEG C, and demulsifier concentration is in the range of 70~120ppm, has more preferable dewatering and desalting effect, especially dense
Best results when being 70 DEG C are spent for 80ppm, dehydration temperaturre.
The demulsifier comparative example 1-3 provided in demulsifier 1-4 prepared by embodiment 1-4 and comparative example 1-3, above-mentioned
Under optium concentration and temperature conditionss, breaking emulsion and dewatering experiment effect is shown in Table 1, and demulsification desalination experiment effect is shown in Table 2.
Table 1
Table 2
Claims (10)
1. a kind of preparation method of polyelectrolyte type crude oil desalting demulsifier, it is characterised in that comprise the following steps：
1) poly glycol monomethyl ether terminal hydroxy group progress amination is obtained into amination modified poly glycol monomethyl ether；
2) preparation of glycidyl dimethyl alkyl ammomium chloride：To N, epoxychloropropane is added dropwise in N- dimethyl alkylamines, rises
Temperature 6~30h of isothermal reaction, reaction product is isolated and purified to 25 DEG C~40 DEG C, obtains glycidyl dimethyl alkyl chlorination
Ammonium；Wherein described N, the carbon chain lengths of alkyl are C in N- dimethyl alkylamines6-C34；
3) quaternary ammonium N, the preparation of O- carboxyalkyl chitosans：By N, O- carboxyalkyls chitosan is dissolved using solvent orange 2 A, adjusted using alkali lye
Save solution ph；The glycidyl dimethyl alkyl ammomium chloride obtained by step 2) is dissolved in solvent orange 2 A again, is added dropwise to reaction
System, 60~80 DEG C are warming up to, after reacting 8~24h, reaction solution is dialysed, be freeze-dried, obtain quaternary ammonium N, O- carboxyalkyl shells
Glycan；
4) modified poly (ethylene glycol) monomethyl ether and quaternary ammonium N, O- carboxyalkyl chitosan reactions：Quaternary ammonium N prepared by step 3), O-
Carboxyalkyl chitosan is dissolved in solvent B, is stirred continuously at room temperature, adds a certain amount of catalyst, by the amination modified of preparation
Poly glycol monomethyl ether is added drop-wise in reaction system after being dissolved in solvent B, is reacted at room temperature 24~48h, separating-purifying, is freeze-dried,
Obtain poly glycol monomethyl ether grafting quaternary ammonium N, O- carboxyalkyl chitosans.
2. the preparation method of polyelectrolyte type crude oil desalting demulsifier according to claim 1, it is characterised in that step 1)
Described in amination modified concretely comprise the following steps：1 molar part poly glycol monomethyl ether is dissolved in solvent C, keeps reaction lazy
Property gaseous environment in, add 1~2 molar part catalyst, then 2.5~5 molar part sulfonylation agents be dissolved in after solvent C and slowly dripped
Be added in reaction solution, ice-water bath reacts 3~5h, is evaporated under reduced pressure and removes solvent, adds solvent D recrystallization, by recrystallized product plus
Enter into 10~20 molar part amination reagents, 140~160 DEG C of 6~8h of back flow reaction, be evaporated under reduced pressure, freeze-drying obtains ammonia
Base polyethylene glycol monomethyl ether；Wherein, the equal molecular mass of the number of the poly glycol monomethyl ether be 350,500,750,1000,
1900 or 5000.
3. the preparation method of polyelectrolyte type crude oil desalting demulsifier according to claim 2, it is characterised in that
Solvent C is one kind in dichloromethane, chloroform, carbon tetrachloride, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide
It is or a variety of；
Solvent D is ether, the one or more in isopropyl ether, methyl tertiary butyl ether(MTBE)；
The catalyst is pyridine or triethylamine；
The sulfonylation agent is paratoluensulfonyl chloride；
The amination reagent is ammoniacal liquor；
The inert gas environment is nitrogen or argon gas.
4. the preparation method of polyelectrolyte type crude oil desalting demulsifier according to claim 1, it is characterised in that
In step 2), the N, the quality parts ratio of N- dimethyl alkylamines and epoxychloropropane is 1.93~2.97：3.7.
5. the preparation method of polyelectrolyte type crude oil desalting demulsifier according to claim 1, it is characterised in that step 3)
In, described N, the preparation method of O- carboxyalkyl chitosans is：
By weight, 1.61 parts of chitosans are swelled, alkali lye regulation suspension are used as alkalescence, under the conditions of -15 DEG C~-25 DEG C
It is stirred overnight, adds 7.4~14.8 parts of carboxylated reagent chloro alkyl acid sodium, be warming up to 30~60 DEG C of 3~12h of stirring reaction,
Reaction product is isolated and purified, freeze-drying obtains N, O- carboxyalkyl chitosans；Wherein, the carbon chain length of the chloro alkyl acid sodium
Spend for C2-C10。
6. the preparation method of polyelectrolyte type crude oil desalting demulsifier according to claim 1, it is characterised in that
In step 3), described N, the quality parts ratio of O- carboxyalkyls chitosan and glycidyl dimethyl alkyl ammomium chloride is
3.21：1.93~7.7；
In step 3), the pH value range is 8~10.
7. the preparation method of polyelectrolyte type crude oil desalting demulsifier according to claim 1, it is characterised in that step 3)
In, by N, after O- carboxyalkyls chitosan is dissolved using solvent orange 2 A and used alkali lye regulation solution ph, then the solution is warming up to
45~50 DEG C, isothermal reaction 1h.
8. the preparation method of polyelectrolyte type crude oil desalting demulsifier according to claim 1, it is characterised in that step 4)
In, the quaternary ammonium N, O- carboxyalkyls chitosan, catalyst, the quality parts ratio of amination poly glycol monomethyl ether for 0.47~
1.05:0.115~0.206:1.75~25.
9. the preparation method of polyelectrolyte type crude oil desalting demulsifier according to claim 1, it is characterised in that step 4)
In, the catalyst is carbodiimides, dicyclohexylcarbodiimide, the one or more in n-hydroxysuccinimide.
10. the preparation method of polyelectrolyte type crude oil desalting demulsifier according to claim 1, it is characterised in that
The solvent orange 2 A is distilled water, isopropanol, sodium hydroxide solution, hydrochloric acid solution, DMF, N, N dimethyl
One or more mixing in acetamide, dimethyl sulfoxide, acetic acid, methanol；
The solvent B is distilled water, isopropanol, sodium hydroxide solution, DMF, DMA,
One or more in dimethyl sulfoxide, acetic acid, methanol.
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| CN103320158A (en) * | 2013-07-10 | 2013-09-25 | 武汉工程大学 | Natural polysaccharide macromolecule-modified crude oil demulsifier |
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| CN1257886A (en) * | 1998-12-18 | 2000-06-28 | 中国科学院成都有机化学研究所 | Process for synthesizing polyether p-toluenesulfonate |
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