CN106188552B - The preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier - Google Patents
The preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of chitosan class natural macromolecule modification crude oil desalting demulsifier.Specific step is as follows: 1) poly glycol monomethyl ether being carried out halogenation modification；2) glycidyl dimethyl alkyl ammomium chloride is prepared；3) quaternized carboxyalkyl chitosan is prepared；4) it by modified poly (ethylene glycol) monomethyl ether and quaternized carboxyalkyl chitosan reaction, obtains target product poly glycol monomethyl ether and is grafted quaternized carboxyalkyl chitosan.The present invention has many advantages, such as from a wealth of 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 demulsifier produced by the present invention, simultaneously because containing a large amount 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 has both the ability of removing oil-soluble salt while demulsification.
Description
Technical field
The present invention relates to a kind of preparation methods of chitosan class natural macromolecule modification crude oil desalting demulsifier, belong to petroleum
Chemical field.
Background technique
With the rapid development of industry, the demand of petroleum is increasing, improves oil recovery with very important
Meaning.Since the usage amount of chemical flooding constantly increases, the heaviness of crude oil and peracid value are got worse in addition, the gold in crude oil
Belong to ion concentration to be gradually increasing.Salt in crude oil is mainly inorganic salts, is mostly dissolved in the water contained by it, and water and oil form surely
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 is adsorbed on oil-water interfaces, forms the viscoplasticity film with some strength, causes dynamics barrier to emulsion droplet coalescence
Hinder, crude oil emulsion is made to be provided with stability.The principle of demulsification is to destroy the factor of emulsion stabilization, both at home and abroad to crude oil demulsification
It studies and more successfully develops many breaking methods.The most commonly used is demulsifier is added, demulsifier is current oil field and refining in oil field
One of essential chemical reagent of factory.With the development of petroleum industry, the demand of demulsifier increasingly increases, and wants 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 is more demanding to equipment and process conditions, implement more complicated, early investment and later period operation
Expense is relatively high；Chemical method is a kind of method of economical rationality.
The demulsification process of demulsifier is generally divided into 3 stages: (1) after crude oil emulsion is added in demulsifier, it being allowed to be dispersed in
In entire oil phase, and it can enter in the droplet being emulsified；(2) demulsifier penetrates into the protective layer of emulsification droplet, and makes protective layer
Fragile crumple destroys, and after protecting damage layer, the droplet being emulsified is close to each other and contacts；(3) droplet coalesces, the droplet 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
It rises, successively develops three generations's demulsifier.The 1920s to the thirties is to solve the demulsification of oil-in-water type crude oil emulsion, is occurred
First generation low molecule ionic demulsifying agent, such as fatty acid salt, naphthenate anionic demulsifier, quaternaries cation
Type demulsifier.This type demulsifier advantage is cheap, the disadvantage is that dosage is big, effect is poor, vulnerable to influence of electrolyte etc..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 are broken to crude oil
Emulsion has carried out a large amount of research, proposes a large amount of patent.It is earliest with alkane as the nonionic surfactant of demulsifier
As hydrophobic group, prepared by a certain number of ethylene oxide of graft copolymerization for base phenol, fatty alcohol.It is big with tertiary oil recovery technology
Scale on-site experiment, novel crude oil demulsifier continue to bring out.Into after the eighties, simple ethylene oxide propylene oxide block polyethers
Demulsifier starts replaced polyamines, polymer-type, amphoteric ion type demulsifier, and minimum amount drops to 100mg/L or less.But
The shortcomings that these demulsifiers is that specificity 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 that the application study of demulsifier has been pushed to a new step.
To solve the above problems, occurring the method that more initiators prepare crude oil demulsifier in recent years.Chinese patent CN
200510130345 describe a kind of polyether-type crude oil demulsifier.Using polyethylene polyamine or nonylphenolic resin as initiator, with
Ethylene oxide, propylene oxide react to obtain polyethers, then polyethers and chain extender, pyridine hybrid reaction are obtained.The invention has preparation
The advantages that simple process, dosage is few, and breaking emulsion and dewatering effect is good, at low cost, but the demulsifier cannot reach low-temperature demulsification to save
The effect of thermal energy.Chinese patent CN 201410710742 describes a kind of low temperature crude oil demulsifier.It is sweet with Glycidyl methacrylate
Grease, Hexafluorobutyl mathacrylate are that initiator and acetone, acrylic acid copolymer obtain.Temperature needed for having evaded existing product demulsification
The drawbacks of degree is high, and the demulsification time is long, is dehydrated water quality inferiority.It can be demulsified at low temperature, reduce ton oil consumption tolerance, save the energy, improve
Economic benefit and equipment treatment effeciency.But the demulsifier specificity is strong, and stability is poor, cannot be suitble to a variety of different types of originals
Oil demulsification.Chinese patent CN 201310289037.6 describes a kind of polysaccharide-modified crude oil demulsifier.It is starting with polysaccharide
Agent, and it is carried out it is quaternised modified, it is polyether graft modified, the demulsifier have it is from a wealth of sources, natural, nontoxic, sustainable, make
Many advantages, such as good with safety.Not only breaking emulsion and dewatering effect is good for the demulsifier, and be demulsified the great amount of hydroxy group etc. contained in agent molecule
Group has certain chelant ability to metal ion, but binding ability is not strong, cannot dehydration while abjection variety classes and
A large amount of metal cation also needs to be improved.Therefore, it is necessary to develop a kind of low-temperature demulsification, fast emulsion breaking expands demulsifier pair
The crude oil scope of application and the demulsifier for having both good dewatering and desalting effect.
Chitin is from a wealth of sources, and content is only second to cellulose, is the organic compound of the second in the world major class.Chitosan is first
The product of shell element deacetylation, containing the amino that reactivity is bigger on strand, is easier to compared with xanthan gum and guar gum
Graft modification.Chitosan class natural polymer has fabulous a biocompatibility and environment friendly, and molecular weight is big, active hydrogen
It is more, have branched structure and unique rheologic behavio(u)r.Its derivative has stronger flocculation ability, occupied by oil-water interfaces
Area it is big, have preferable temperature tolerance, higher interfacial activity, be the splendid candidate target of demulsifier initiator.Shell is poly-
Carboxyalkyl and quaternary ammonium salt group are introduced into sugar subchain very the electronegative ion such as metal cation, cycloalkanes acid group in crude oil
Strong binding ability.Pass through the position of each substituent group of control and degree of substitution and polyether lateral chain, carboxyalkyl group and quaternary ammonium simultaneously
A series of high-efficient demulsifiers for being appropriate to heterogeneity crude oil can be obtained in the length of segment on salt groups, and can be in demulsification
Oil-soluble salt is sloughed simultaneously.
Summary of the invention
The purpose of the present invention is propose a kind of chitosan class natural polymer for above-mentioned problems of the prior art
The preparation method of sub- crude oil modified desalination demulsifier obtains a series of high-efficient demulsifiers for being appropriate to heterogeneity crude oil, and can
To slough oil-soluble salt while demulsification.
To achieve the above object, present invention provide the technical scheme that
The preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier, which is characterized in that including following step
It is rapid:
1) the progress halogenation of poly glycol monomethyl ether terminal hydroxy group is obtained into halogenation modification poly glycol monomethyl ether；
2) to N, epoxy chloropropionate the preparation of glycidyl dimethyl alkyl ammomium chloride: is added dropwise in N- dimethyl alkylamine
Alkane is warming up to 25 DEG C~40 DEG C, and 6~30h of isothermal reaction isolates and purifies reaction product, obtains glycidyl dimethyl alkane
Ammonium chloride；The carbon chain lengths of alkyl are C in the wherein N, N- dimethyl alkylamine6‐C34；
3) preparation of quaternized carboxyalkyl chitosan: carboxyalkyl chitosan is dissolved using solvent A, is adjusted using lye molten
Liquid pH value；The resulting glycidyl dimethyl alkyl ammomium chloride of step 2) is dissolved in solvent A again, is added dropwise to reactant
System, be warming up to 60~80 DEG C reaction 8~for 24 hours after, reaction solution is dialysed, be freeze-dried, obtain the quaternized carboxyalkyl of solid product
Chitosan；
4) modified poly (ethylene glycol) monomethyl ether and quaternized carboxyalkyl chitosan reaction: by the resulting quaternized carboxylic alkane of step 3)
Base enclosure glycan is dissolved in solvent B, and stirring is warming up to 60~100 DEG C；By the resulting halogenation modification polyethyleneglycol first of step 1)
Ether is dissolved using solvent B, is added drop-wise in reaction system, 24~48h of isothermal reaction is isolated and purified, and obtains target product chitosan class
Natural macromolecule modification crude oil desalting demulsifier poly glycol monomethyl ether is grafted quaternized carboxyalkyl chitosan.
According to the above scheme, it is preferable that the specific steps of the step 1) halogenation modification are as follows: by the poly- second two of 0.5~1 molar part
Alcohol monomethyl ether is dissolved in solvent C, is stirred under the conditions of 0~5 DEG C of ice-water bath, 1~2 molar part catalyst is added, by 1~2 mole
Part chlorination or bromide reagent are slowly dropped in reaction solution, heating reflux reaction, and temperature is 60~90 DEG C, time 2-12h,
Reaction solution is isolated and purified, and freeze-drying obtains chlorination or bromination poly glycol monomethyl ether；Wherein, the poly glycol monomethyl ether
Number average molecular weight be 350,500,750,1000,1900 or 5000.Preferably, the solvent C is carbon tetrachloride, dichloromethane
Alkane, chloroform, Isosorbide-5-Nitrae-dioxane, n,N-Dimethylformamide, one of n,N-dimethylacetamide, acetonitrile and toluene or
It is a variety of.Preferably, the catalyst is pyridine or triethylamine.Preferably, the chlorination or bromide reagent are thionyl chloride, bromine
Change one of sulfoxide, phosgene, oxalyl chloride, α-bromination propionyl bromide, phosphorus tribromide.It is preferably, described to isolate and purify specifically:
Solvent is removed by vacuum distillation, dissolves distillation residual solids with methylene chloride, washing is taken out after anhydrous sodium sulfate water removal is added
Filter, filtrate decompression distill to obtain solid.
According to the above scheme, it is preferable that the specific steps of the step 1) halogenation modification are as follows: by the poly- second two of 0.5~1 molar part
Alcohol monomethyl ether is dissolved in solvent C, is stirred under the conditions of 0~5 DEG C of ice-water bath, be added 0.75~1.5 molar part catalyst and 0.5~
0.1~0.2 molar part potassium iodide reagents are slowly dropped in reaction solution, react 2- at room temperature by 1 molar part sulfonylation agent
12h, reaction solution are isolated and purified, and freeze-drying obtains iodo poly glycol monomethyl ether；Wherein, the poly glycol monomethyl ether
Number average molecular weight is 350,500,750,1000,1900 or 5000.Preferably, the solvent C is carbon tetrachloride, dichloromethane
Alkane, chloroform, Isosorbide-5-Nitrae-dioxane, n,N-Dimethylformamide, one of n,N-dimethylacetamide, acetonitrile and toluene or
It is a variety of.Preferably, the catalyst is silver oxide.Preferably, the sulfonylation agent is paratoluensulfonyl chloride.Preferably, institute
It states and isolates and purifies specifically: reaction solution is filtered to remove silver oxide, solvent is removed by vacuum distillation, remaining mixture is added
Into acetonitrile, 60 DEG C are warming up to, persistently stirs 2h, reaction solution carries out column chromatography by the mobile phase of methylene chloride and methyl alcohol mixed liquor
Separation.
According to the above scheme, it is preferable that in step 2), the N, the mass fraction of N- dimethyl alkylamine and epoxychloropropane
Than for 1.93~2.97:3.7.
According to the above scheme, it is preferable that described to isolate and purify to be dried in vacuo after being eluted with acetone in step 2).
According to the above scheme, it is preferable that the preparation method of carboxyalkyl chitosan described in step 3) is:
By weight, 1.61 parts of chitosans are swollen, lye is used to adjust suspension for alkalinity, in -15 DEG C~-25 DEG C items
Be stirred overnight under part, 7.4~14.8 parts of carboxylated reagent chloro alkyl acid sodium be added, be warming up to 30~60 DEG C be stirred to react 3~
12h isolates and purifies reaction product, and freeze-drying obtains carboxyalkyl chitosan；Wherein, the carbon chain length of the chloro alkyl acid sodium
Degree is C2-C10.Preferably, described to isolate and purify specifically: filtering, by obtained solid product 80% ethyl alcohol and dehydrated alcohol
It is drying for one day in 60 DEG C after rinsing respectively, then dialyse after solid is dissolved in water.
According to the above scheme, it is preferable that in step 3), the carboxyalkyl chitosan and glycidyl dimethyl alkyl chloride
The mass parts ratio for changing ammonium is 3.21:1.93~7.7.
According to the above scheme, it is preferable that in step 3), the pH value range is 8~10.
According to the above scheme, it is preferable that in step 3), carboxyalkyl chitosan is being dissolved using solvent A and is using lye tune
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 sufficiently opened, and is grafted more uniform.
According to the above scheme, it is preferable that in step 3), the solvent A is distilled water, isopropanol, sodium hydroxide solution, salt
Acid solution, n,N dimethylformamide, N, N dimethyl acetamide, dimethyl sulfoxide, acetic acid, mixing one or more in methanol.
According to the above scheme, it is preferable that in step 4), the quaternized carboxyalkyl chitosan and halogenation modification polyethylene glycol
The mass parts ratio of monomethyl ether are as follows: 0.47~1.05:0.35~5.
According to the above scheme, it is preferable that in step 4), the solvent B be distilled water, isopropanol, sodium hydroxide solution, N,
One of dinethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, acetic acid, methanol, acetonitrile or a variety of mixing.
According to the above scheme, it is preferable that in step 4), when the modified poly (ethylene glycol) monomethyl ether for participating in this step reaction is chlorination
Or when the modified poly glycol monomethyl ether of bromination, before the operation of the stirring heating, also use lye adjust its pH value of solution for
Alkalinity, and catalyst potassium iodide is added.
According to the above scheme, it is preferable that in step 4), the specific steps isolated and purified are as follows:
Vacuum distillation, dialysis, freeze-drying are (when the modified poly (ethylene glycol) monomethyl ether for participating in this step reaction is chlorination or bromine
When changing modified poly glycol monomethyl ether)；Alternatively,
Vacuum distillation, remaining solid are washed with methylene chloride, are added mixture in the acetic acid solution of 10mL 50%,
4h is stirred at room temperature, then reaction solution is poured into the ethyl alcohol and ether mixed solution of 500mL ice, precipitates filtering acetone washing,
Freeze-drying (when the modified poly (ethylene glycol) monomethyl ether for participating in this step reaction is iodo poly glycol monomethyl ether).
According to the above scheme, it is preferable that in each step, the lye is sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid
One of potassium is a variety of.
Synthetic route of the invention is as follows:
1, poly glycol monomethyl ether is modified:
2, prepared by glycidyl dimethyl alkyl ammomium chloride:
3, chitosan carboxylation alkylation is modified, and quaternised modified product is reacted with modified poly (ethylene glycol) monomethyl ether:
In the prior art, traditional polyether type demulsifying agent is usually using ethylene oxide, propylene oxide as primary raw material, selection tool
The substance for having active hydrogen is initiator, obtains block polymer demulsifier by polymerizeing etherificate；As oilfield exploitation enters the later period, greatly
Amount compound drive largely uses in recovery process, the difficulty that this process exacerbates emulsification of crude oil degree, increases demulsification, and block is poly-
The demulsification performance of ether demulsifier is limited.Compared with prior art, the present invention having the following beneficial effects:
1) present invention has from a wealth of 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) pass through poly glycol monomethyl ether, chlorine alkyl acid sodium, the modification of glycidyl dimethyl alkyl ammomium chloride obtains
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
Chitin modified natural polymer demulsifier of the invention has good dewatering and desalting effect；
3) in the present invention, when preparing carboxyalkyl chitosan, the method to be alkalized by low temperature can make hydrogen in chitosan molecule
Key is easier to be opened, and lye is easier to penetrate into chitosan molecule, and then carboxyalkyl side chain is more uniformly grafted to shell and gathers
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 alkylamine, polyethers, perhaps change reaction raw materials amount ratio or change
The conditions such as the reaction temperature of reaction system and time, to change demulsifier molecular structure such as molecular weight, degree of substitution, hydrophobic segment
Length aggregated structure etc., and then regulate and control the desalting and dewatering effect of the high-efficient demulsifier of synthesis, it is (different to be suitable for heterogeneity
The place of production, saliferous water content are different) crude oil.
Specific embodiment
For a better understanding of the present invention, below 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 chitosan class natural macromolecule modification crude oil desalting demulsifier, specifically comprises the following steps:
(1) poly glycol monomethyl ether terminal hydroxy group is chlorination modified: taking polyethylene glycol monomethyl ether (Mn=350) 1.75g
(5mmol) is dissolved in 40mL Isosorbide-5-Nitrae-dioxane, is stirred under ice-water bath condition (0 DEG C), and 0.79g (10mmol) pyridine is added
With 1.19g (10mmol) thionyl chloride, in 70 DEG C of back flow reaction 2h.Solvent is removed by vacuum distillation, is dissolved with methylene chloride
Residual solids are distilled, are washed 3 times, are filtered after anhydrous sodium sulfate water removal is added, filtrate decompression distills to obtain solid, is freeze-dried
To chloro poly glycol monomethyl ether；
(2) prepared by glycidyl dimethyl lauryl ammonium chloride: to equipped with blender, dropping funel and condensing reflux
2.13g Dodecyl Dimethyl Amine is added in the three-necked flask of device, is stirred continuously, 3.7g epoxychloropropane is taken to pass through dropping liquid
Funnel is added dropwise to complete in 30min, is kept for 25 DEG C of temperature, isothermal reaction 6h.Stop reaction, product is eluted with acetone, and vacuum is dry
It is dry, obtain glycidyl dimethyl lauryl ammonium chloride.
(3) preparation of carboxymethyl chitosan: 1.61g chitosan is added in the flask of 250mL, and 10mL isopropanol is added
The sodium hydroxide solution of 2.5mL 10mol/L is added in swelling, continues to stir 30min, be stirred overnight under the conditions of -15 DEG C, is added
7.4g sodium chloroacetate heats reaction mixture and to 60 DEG C and continues to be stirred to react 3h after adding completely.Filtering is anti-after the reaction was completed
Mixture is answered to obtain crude product, 80% ethyl alcohol of product and dehydrated alcohol wash 3 times respectively, are put into 60 DEG C of drying box dry
After one day, solid is dissolved in water and is dialysed 3 days, n,O-carboxymethyl chitosan is freeze-dried to obtain；
(4) preparation of quaternized carboxymethyl chitosan: 3.21g n,O-carboxymethyl chitosan is weighed in three-necked flask, is added
Enter 40mL distilled water, adjusts 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, and 8h is reacted.Instead
After the completion of answering, reaction solution is dialysed 3~5 days, freeze-drying obtains the quaternized carboxymethyl chitosan of solid product；
(5) modified poly (ethylene glycol) monomethyl ether is reacted with quaternized carboxymethyl chitosan: taking the quaternized carboxymethyl chitosan of 0.47g
Sugar is placed in 250mL three-necked flask, and 30mL dimethyl sulfoxide solution is added, and 0.8g potash solid and 0.166g iodine are added after dissolution
Change potassium, stirring is warming up to 80 DEG C, by 0.35g chlorinated polyethylene glycol monomethyl ether (Mn=350) it is dissolved in 10mL dimethyl sulfoxide solution,
It is added dropwise to complete in 10min, reaction for 24 hours, is evaporated under reduced pressure concentration of reaction solution, is dialysed 3 days with bag filter, and Liquid Residue is freeze-dried in bag
It is demulsifier 1 up to the quaternized carboxymethyl chitosan of target product-poly glycol monomethyl ether grafting.
Embodiment 2
A kind of preparation of chitosan class natural macromolecule modification crude oil desalting demulsifier, specifically comprises the following steps:
(1) bromination of poly glycol monomethyl ether terminal hydroxy group is modified: taking polyethylene glycol monomethyl ether (Mn=750) 3.75g
(5mmol) is dissolved in 40mL Isosorbide-5-Nitrae-dioxane, is stirred under ice-water bath condition (2 DEG C), and 1.18g (15mmol) pyridine is added
With 1.78g (15mmol) thionyl bromide, in 70 DEG C of back flow reaction 4h.Solvent is removed by vacuum distillation, is dissolved with methylene chloride
Residual solids are distilled, are washed 3 times, are filtered after anhydrous sodium sulfate water removal is added, filtrate decompression is distilled off solvent and obtains solid, cold
Jelly is dried to obtain bromo poly glycol monomethyl ether.
(2) prepared by glycidyl dimethyl tetradecyl ammonium chloride: to equipped with blender, dropping funel and condensing reflux
2.41g dodecyldimethylamine base tertiary amine is added in the three-necked flask of device, is stirred continuously, 3.7g epoxychloropropane is taken to pass through dropping liquid
Funnel is added dropwise to complete in 30min, is kept for 30 DEG C of temperature, isothermal reaction 20h.Stop reaction, product is eluted with acetone, and vacuum is dry
It is dry, obtain glycidyl dimethyl tetradecyl ammonium chloride.
(3) preparation of carboxyetbyl chitosan: 1.61g chitosan is added in the flask of 250mL, and 10mL isopropanol is added
The sodium hydroxide solution of 2.5mL 10mol/L is added in swelling, continues to stir 30min, be stirred overnight under the conditions of -20 DEG C, is added
8.2g chloropropionic acid sodium heats reaction mixture and to 60 DEG C and continues to be stirred to react 4h after adding completely.Filtering is anti-after the reaction was completed
Mixture is answered to obtain solid product, 80% ethyl alcohol of product and dehydrated alcohol wash 3 times respectively, are put into 60 DEG C of drying box and do
It is dry, then dialyse 5 days after solid is dissolved in water, it is freeze-dried to obtain solid product N, O- carboxyetbyl chitosan.
(4) preparation of quaternized carboxyetbyl chitosan: weighing 3.21g N, and O- carboxyetbyl chitosan adds in three-necked flask
Enter 40mL distilled water, adjusts 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 reaction was completed, reaction solution is dialysed 5 days, and freeze-drying obtains the quaternized carboxyetbyl chitosan of solid product.
(5) modified poly (ethylene glycol) monomethyl ether is reacted with quaternized carboxyetbyl chitosan: taking the quaternized carboxyethyl shell of 0.53g poly-
Sugar is placed in 250mL three-necked flask, and 30mL dimethyl sulfoxide solution is added, and 0.8g potash solid and 0.166g iodine are added after dissolution
Change potassium, stirring is warming up to 90 DEG C, 1.5g bromination poly glycol monomethyl ether (Mn=750) is dissolved in 10mL dimethyl sulfoxide solution,
It is added dropwise to complete in 10min, reacts 30h, be evaporated under reduced pressure concentration of reaction solution, dialysed 3 days with bag filter, Liquid Residue is freeze-dried in bag
It is demulsifier 2 up to the quaternized carboxyetbyl chitosan of target product-poly glycol monomethyl ether grafting.
Embodiment 3
A kind of preparation of chitosan class natural macromolecule modification crude oil desalting demulsifier, specifically comprises the following steps:
(1) iodate of poly glycol monomethyl ether terminal hydroxy group is modified: taking polyethylene glycol monomethyl ether (Mn=1000) 5g (5mmol)
It is dissolved in 40mL toluene, is stirred under ice-water bath condition (5 DEG C), 1.73g (7.5mmol) silver oxide, 0.166g (1mmol) is added
Potassium iodide and 1g (5mmol) paratoluensulfonyl chloride, react 12h at room temperature.It is filtered to remove silver oxide, is removed by vacuum distillation molten
Remaining mixture is added in 30mL acetonitrile by agent, is warming up to 60 DEG C, is persistently stirred 2h.Reaction solution is by methylene chloride and methanol
Mobile phase carry out column chromatography for separation, freeze-drying obtain iodo poly glycol monomethyl ether.
(2) prepared by glycidyl dimethyl cetyl chloride ammonium: to equipped with blender, dropping funel and condensing reflux
2.69g hexadecyldimethyl benzyl ammonium tertiary amine is added in the three-necked flask of device, is stirred continuously, takes 3.7g epoxychloropropane and use dropping liquid
Funnel is added dropwise to complete in 30min, 40 DEG C of temperature of holding, after isothermal reaction 30h, stops reaction.Product acetone washing, vacuum
It is dry, obtain glycidyl dimethyl cetyl chloride ammonium.
(3) preparation of carboxylic propyl chitosan: 1.61g chitosan is added in the flask of 250mL, and 10mL isopropanol is added
The sodium hydroxide solution of 2.5mL 10mol/L is added in swelling, continues to stir 30min, be stirred overnight under the conditions of -25 DEG C, is added
9.5g chloro-butyric acid sodium heats reaction mixture and to 30 DEG C and continues to be stirred to react 12h after adding completely.Filtering is anti-after the reaction was completed
Mixture is answered to obtain solid product, 80% ethyl alcohol of product and dehydrated alcohol wash 3 times respectively, are put into 60 DEG C of drying box and do
It is dry, then dialyse 4 days after solid is dissolved in water, it is freeze-dried to obtain solid product N, O- carboxylic propyl chitosan.
(4) preparation of quaternized carboxylic propyl chitosan: weighing 3.21g N, and O- carboxylic propyl chitosan adds in three-necked flask
Enter 40mL distilled water, adjusts 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,
Reaction is for 24 hours.After the reaction was completed, reaction solution is dialysed 5 days, and freeze-drying obtains the quaternized carboxylic propyl chitosan of solid product.
(5) modified poly (ethylene glycol) monomethyl ether and quaternized carboxylic propyl chitosan reaction: take the quaternized carboxylic propyl shell of 0.64g poly-
Sugar is placed in 250mL three-necked flask, 30mL acetonitrile solution is added, magnetic agitation is warming up to 60 DEG C, by 2g iodate polyethyleneglycol
Methyl ether (Mn=1000) is dissolved in 10mL acetonitrile, is added dropwise to complete in 10min, and reaction is for 24 hours.Vacuum distillation, remaining solid dichloro
Methane wash several times, adds mixture in the acetic acid solution of 10mL 50%, stirs 4h at room temperature.Reaction solution is poured into
In the ethyl alcohol and ether mixed solution of 500mL ice, precipitating filtering with acetone washing several times after, be freeze-dried up to target product-
The quaternized carboxylic propyl chitosan of poly glycol monomethyl ether grafting is demulsifier 3.
Embodiment 4
A kind of preparation of chitosan class natural macromolecule modification crude oil desalting demulsifier, specifically comprises the following steps:
(1) poly glycol monomethyl ether terminal hydroxy group is chlorination modified: taking polyethylene glycol monomethyl ether (Mn=5000) 5g (1mmol)
It is dissolved in 40mL Isosorbide-5-Nitrae-dioxane, is stirred under ice-water bath condition (0 DEG C), 0.158g (2mmol) pyridine and 0.252g is added
(2mmol) oxalyl chloride, in 90 DEG C of back flow reaction 12h.Solvent is removed by vacuum distillation, it is solid to dissolve distillation residual with methylene chloride
Body is washed 3 times, is filtered after anhydrous sodium sulfate water removal is added, and filtrate decompression distills to obtain solid, and freeze-drying obtains the poly- second of chloro
Glycol monomethyl ether；
(2) prepared by glycidyl dimethyl dotriacontane ammonium chloride: to blender is equipped with, dropping funel and being condensed back to
It flows and 2.97g dotriacontyl dimethyl tertiary amine is added in the three-necked flask of device, be stirred continuously, 3.7g epoxychloropropane is taken to pass through
Dropping funel is added dropwise to complete in 30min, is kept for 40 DEG C of temperature, isothermal reaction 30h.Stop reaction, product is eluted with acetone, very
Sky is dry, obtains glycidyl dimethyl dotriacontane ammonium chloride.
(3) preparation of carboxylic nonyl chitosan: 1.61g chitosan is added in the flask of 250mL, and 10mL isopropanol is added
The sodium hydroxide solution of 2.5mL 10mol/L is added in swelling, continues to stir 30min, be stirred overnight under the conditions of -20 DEG C, is added
14.8g chlorine sodium caprate heats reaction mixture and to 60 DEG C and continues to be stirred to react 3h after adding completely.Filtering is anti-after the reaction was completed
Mixture is answered to obtain crude product, 80% ethyl alcohol of product and dehydrated alcohol wash 3 times respectively, are put into 60 DEG C of drying box dry
After one day, solid is dissolved in water and is dialysed 3 days, N, O- carboxylic nonyl chitosan are freeze-dried to obtain；
(4) preparation of quaternized carboxylic nonyl chitosan: 3.21g n,O-carboxymethyl chitosan is weighed in three-necked flask, is added
Enter 40mL dimethyl sulfoxide, adjust pH=8~10 with sodium hydroxide solution, be warming up to 50 DEG C, isothermal reaction 1h (allows carboxymethyl chitosan
Sugar chain is sufficiently opened, and is grafted more uniform)；7.7g glycidyl dotriacontane ammonium chloride is dissolved in 20mL dimethyl sulfoxide
In, it is added drop-wise in reaction system, is heated up 80 DEG C by constant pressure funnel, react 8h.After the reaction was completed, by reaction solution dialysis 3~5
It, freeze-drying obtains the quaternized carboxylic nonyl chitosan of solid product；
(5) modified poly (ethylene glycol) monomethyl ether and quaternized carboxylic nonyl chitosan reaction: take the quaternized carboxylic nonyl shell of 1.05g poly-
Sugar is placed in 250mL three-necked flask, and 30mL dimethyl sulfoxide solution is added, and 0.8g potash solid and 0.166g iodine are added after dissolution
Change potassium, stirring is warming up to 80 DEG C, by 5g chlorinated polyethylene glycol monomethyl ether (Mn=5000) it is dissolved in 10mL dimethyl sulfoxide solution,
It is added dropwise to complete in 10min, reacts 48h, be evaporated under reduced pressure concentration of reaction solution, dialysed 3 days with bag filter, Liquid Residue is freeze-dried in bag
It is demulsifier 4 up to the quaternized carboxylic nonyl chitosan of target product-poly glycol monomethyl ether grafting.
Comparative example 1
Quaternized carboxymethyl chitosan made from step (4) is as demulsifier comparative example 1 in Example 1.
Comparative example 2
According to a kind of shell made from the method for embodiment 1 in the bulletin text of Chinese patent application CN201310289037.6
The crude oil demulsifier of glycans natural macromolecule modification is as demulsifier comparative example 2.
Comparative example 3
It is JL series demulsifier as demulsifier comparative example 3 using commercially available trade names.
Demulsifying effect of demulsifier experiment
Be demulsified experiment oil using the crude oil that Wuhan Branch, Sinopec Corp. provides as the present invention
It is tested, is measured by GB/T 8929-88 (way of distillation), measuring water content in crude oil is 50%.
Dehydration temperaturre is set as 60~80 DEG C, demulsifier concentration is 70~120ppm in crude oil.Referring to Chinese people's republicanism
State oil and gas industry standard SY/T 5281-2000 " crude oil demulsifier service performance detection method (bottle examination method) " is right respectively
The demulsification performance of demulsifier comparative example 1-3 made from demulsifier 1-4 made from embodiment 1-4 and comparative example is tested,
The concussion method of dehydration test bottle is using mechanical concussion method in test.
Specific step is as follows: crude oil emulsion sample being poured into 100mL tool plug graduated cylinder, 30min is heated in water bath with thermostatic control；With
A certain amount of crude oil demulsification agent solution is added into tool plug graduated cylinder in pipette；Using mechanical concussion method, amplitude is greater than 20cm, concussion
Time is 5min, and after mixing well, tool plug graduated cylinder is replaced in 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 grease
State of interface.
Experimental result is shown, compared to demulsifier comparative example 1-3, the demulsifier 1-4 obtained according to the method for the present invention is de-
Coolant-temperature gage is 60~80 DEG C, and demulsifier concentration is to have better dewatering and desalting effect, especially dense within the scope of 70~120ppm
Effect is best when degree is 90ppm, dehydration temperaturre is 65 DEG C.
The demulsifier comparative example 1-3 provided in the demulsifier 1-4 and comparative example 1-3 of embodiment 1-4 preparation, above-mentioned
Under the conditions of optium concentration and temperature, 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. the preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier, which comprises the following steps:
1) the progress halogenation of poly glycol monomethyl ether terminal hydroxy group is obtained into halogenation modification poly glycol monomethyl ether；
2) preparation of glycidyl dimethyl alkyl ammomium chloride: to N, being added dropwise epoxychloropropane in N- dimethyl alkylamine, rises
For temperature to 25 DEG C~40 DEG C, 6~30h of isothermal reaction isolates and purifies reaction product, obtains glycidyl dimethyl alkyl chlorination
Ammonium；The carbon chain lengths of alkyl are C in the wherein N, N- dimethyl alkylamine6-C34；
3) quaternary ammonium N, the preparation of O- carboxyalkyl chitosan: by N, O- carboxyalkyl chitosan is dissolved using solvent A, using lye tune
Save solution ph；The resulting glycidyl dimethyl alkyl ammomium chloride of step 2) is dissolved in solvent A again, is added dropwise to reaction
System, be warming up to 60~80 DEG C reaction 8~for 24 hours after, reaction solution is dialysed, be freeze-dried, obtain quaternary ammonium N, O- carboxyalkyl shell
Glycan；
4) modified poly (ethylene glycol) monomethyl ether and quaternary ammonium N, O- carboxyalkyl chitosan reaction: by the resulting quaternary ammonium N of step 3), O-
Carboxyalkyl chitosan is dissolved in solvent B, and stirring is warming up to 60~100 DEG C, by the resulting halogenation modification polyethylene glycol of step 1)
Using being added drop-wise in reaction system after solvent B dissolution, 24~48h of isothermal reaction is isolated and purified monomethyl ether, and it is poly- to obtain target product shell
Carbohydrate natural macromolecule modification crude oil desalting demulsifier poly glycol monomethyl ether is grafted quaternary ammonium N, O- carboxyalkyl chitosan.
2. the preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier according to claim 1, special
Sign is the specific steps of the step 1) halogenation modification are as follows:
0.5~1 molar part poly glycol monomethyl ether is dissolved in solvent C, is stirred under the conditions of 0~5 DEG C of ice-water bath, is added 1~2
1~2 molar part chlorination or bromide reagent are slowly dropped in reaction solution, heating reflux reaction, temperature by molar part catalyst
It is 60~90 DEG C, time 2-12h, reaction solution is isolated and purified, and freeze-drying obtains chlorination or bromination poly glycol monomethyl ether；
Wherein, the number average molecular weight of the poly glycol monomethyl ether is 350,500,750,1000,1900 or 5000.
3. the preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier according to claim 1, special
Sign is the specific steps of the step 1) halogenation modification are as follows:
0.5~1 molar part poly glycol monomethyl ether is dissolved in solvent C, is stirred under the conditions of 0~5 DEG C of ice-water bath, is added 0.75
~1.5 molar part catalyst and 0.5~1 molar part sulfonylation agent, 0.1~0.2 molar part potassium iodide reagents are slowly added dropwise
Into reaction solution, 2-12h is reacted at room temperature, and reaction solution is isolated and purified, and freeze-drying obtains iodo poly glycol monomethyl ether；Its
In, the number average molecular weight of the poly glycol monomethyl ether is 350,500,750,1000,1900 or 5000.
4. the preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier according to claim 2, special
Sign is:
The solvent C is carbon tetrachloride, methylene chloride, chloroform, Isosorbide-5-Nitrae-dioxane, n,N-Dimethylformamide, N, N- bis-
One of methylacetamide, acetonitrile and toluene are a variety of；
The catalyst is pyridine or triethylamine；
The chlorination or bromide reagent is thionyl chloride, thionyl bromide, phosgene, oxalyl chloride, α-bromination propionyl bromide, tribromo
Change one of phosphorus；
In step 4), lye is also used to adjust its pH value of solution as alkalinity before stirring heating, and catalyst potassium iodide is added；
In step 4), it is described isolate and purify the specific steps are vacuum distillation, dialysis, freeze-dryings.
5. the preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier according to claim 3, special
Sign is:
The solvent C is carbon tetrachloride, methylene chloride, chloroform, Isosorbide-5-Nitrae-dioxane, n,N-Dimethylformamide, N, N- bis-
One of methylacetamide, acetonitrile and toluene are a variety of；
The catalyst is silver oxide；
The sulfonylation agent is paratoluensulfonyl chloride；
It is isolated and purified described in halogenation modification specifically: reaction solution is filtered to remove silver oxide, solvent is removed by vacuum distillation,
Remaining mixture is added in acetonitrile, is warming up to 60 DEG C, persistently stirs 2h, reaction solution is by methylene chloride and methyl alcohol mixed liquor
Mobile phase carries out column chromatography for separation；
In step 4), the specific steps isolated and purified are as follows: vacuum distillation, remaining solid are washed with methylene chloride, will be mixed
Object is added in acetic acid solution, is stirred 4h at room temperature, then reaction solution is poured into the ethyl alcohol and ether mixed solution of ice, was precipitated
Filter acetone washing, freeze-drying.
6. the preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier according to claim 1, special
Sign is, in step 2), the N, the mass parts ratio of N- dimethyl alkylamine and epoxychloropropane is 1.93~2.97:3.7.
7. the preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier according to claim 1, special
Sign is N described in step 3), and the preparation method of O- carboxyalkyl chitosan is:
By weight, 1.61 parts of chitosans are swollen, lye is used to adjust suspension for alkalinity, under the conditions of -15 DEG C~-25 DEG C
It is stirred overnight, 7.4~14.8 parts of carboxylated reagent chloro alkyl acid sodium is added, is warming up to 30~60 DEG C and is stirred to react 3~12h,
Reaction product is isolated and purified, freeze-drying obtains N, O- carboxyalkyl chitosan；Wherein, the carbon chain length of the chloro alkyl acid sodium
Degree is C2-C10。
8. the preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier according to claim 1, special
Sign is, in step 3),
The mass parts ratio of the N, O- carboxyalkyl chitosan and glycidyl dimethyl alkyl ammomium chloride is 3.21:1.93
~7.7；
The pH value range is 8~10；
The solvent A is distilled water, isopropanol, sodium hydroxide solution, hydrochloric acid solution, n,N dimethylformamide, N, N dimethyl
Acetamide, dimethyl sulfoxide, acetic acid, mixing one or more in methanol.
9. the preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier according to claim 1, special
Sign is, in step 3), by N, and after O- carboxyalkyl chitosan dissolve using solvent A and is used lye adjusting solution ph, then
The solution is warming up to 45~50 DEG C, isothermal reaction 1h.
10. the preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier according to claim 1, special
Sign is, in step 4),
The quaternary ammonium N, the mass parts ratio of O- carboxyalkyl chitosan and halogenation modification poly glycol monomethyl ether are as follows: 0.47~
1.05:0.35~5；
The solvent B be distilled water, isopropanol, sodium hydroxide solution, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide,
One of dimethyl sulfoxide, acetic acid, methanol, acetonitrile or a variety of mixing.
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| CN108865220B (en) * | 2018-07-20 | 2020-10-23 | 武汉工程大学 | Chitosan oil-in-water crude oil demulsifier and preparation method thereof |
| CN108865224B (en) * | 2018-07-20 | 2020-11-27 | 武汉工程大学 | Polyether grafted oil-in-water crude oil demulsifier and preparation method thereof |
| CN108913201B (en) * | 2018-07-20 | 2020-11-27 | 武汉工程大学 | Crude oil demulsifier and preparation method thereof |
| CN112940147B (en) * | 2021-02-04 | 2022-03-04 | 扬州工业职业技术学院 | Modifier and application thereof in preparation of dicyandiamide-formaldehyde resin |
| CN112961345B (en) * | 2021-02-07 | 2022-09-20 | 威海金钰环保科技有限公司 | Chitosan-based hyperbranched polyamidoamine for demulsification of oil-in-water wastewater and quaternary ammonium salt thereof |
| CN113621092B (en) * | 2021-08-04 | 2022-11-25 | 山东建筑大学 | Microbubble surface function modifier and preparation method thereof |
| CN115651095B (en) * | 2022-09-14 | 2024-02-23 | 中海油能源发展股份有限公司 | Waterproof locking agent for drilling well and preparation method thereof |
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