CN106279708B - A kind of preparation method of chitosan quasi-oil desalination demulsifier - Google Patents
A kind of preparation method of chitosan quasi-oil desalination demulsifier Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of chitosan quasi-oil desalination demulsifier.Specific step is as follows: (1) poly glycol monomethyl ether being carried out epoxidation modification；(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 poly glycol monomethyl ether and are 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 the demulsifier being prepared, 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 quasi-oil desalination demulsifier, belong to petrochemical industry.
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
CN200510130345 describes a kind of polyether-type crude oil demulsifier.Using polyethylene polyamine or nonylphenolic resin as initiator,
It reacts to obtain polyethers with ethylene oxide, propylene oxide, then polyethers and chain extender, pyridine hybrid reaction is obtained.The invention has system
The advantages that standby 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
Save the effect of thermal 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
The drawbacks of temperature 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, mention
High 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
Crude 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 quasi-oil desalination for above-mentioned problems of the prior art
The preparation method of demulsifier, obtain it is a series of be appropriate to heterogeneity crude oil, and oil-soluble salt can be sloughed while demulsification
High-efficient demulsifier.
To achieve the above object, technical solution provided by the invention is as follows:
A kind of preparation method of chitosan quasi-oil desalination demulsifier, which comprises the steps of:
1) poly glycol monomethyl ether terminal hydroxy group progress epoxidation is obtained into epoxidation 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；It is added dropwise to reaction system after the resulting glycidyl dimethyl alkyl ammomium chloride of step 2) is dissolved in solvent A again,
It is warming up to 60~80 DEG C, after reaction 8~for 24 hours, 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 prepared by step (3)
Lye adjusting pH value of solution is added after being dissolved in solvent B in alkyl chitosan, is warming up to 80~100 DEG C, keeps reaction in inert gas ring
It is added drop-wise in reaction system in border, then after epoxidation modification poly glycol monomethyl ether made from step 1) is dissolved in solvent B, it is permanent
Temperature 24~48h of reaction, is evaporated under reduced pressure concentration of reaction solution, is washed three times, the reaction solution of concentration is dialysed 3~5 days, in bag with solvent
Liquid Residue freeze-drying obtains target product natural polymer crude oil demulsifier-poly glycol monomethyl ether and is grafted quaternized carboxylic alkane
Base enclosure glycan.
In above scheme, it is preferable that specific step is as follows for step 1) the epoxidation modification poly glycol monomethyl ether: will
1 molar part poly glycol monomethyl ether is dissolved in solvent C, is added appropriate solvent D and 1~4 molar part alkalizing agent, is warming up to 20
~30 DEG C, 2~6h is reacted, 1~10 molar part epoxidation reagent is slowly dropped in reaction solution, is warming up to 20~40 DEG C, instead
6-20h is answered, for reaction solution after isolating and purifying, freeze-drying obtains epoxidation poly glycol monomethyl ether；Wherein, the polyethylene glycol
The number average molecular weight of monomethyl ether is 350,500,750,1000,1900 or 5000.Preferably, the solvent C is dry toluene.
Preferably, the solvent D is tetrahydrofuran, ethyl alcohol, sodium hydroxide, methylene chloride, n,N-Dimethylformamide and N, N- diformazan
One of yl acetamide is a variety of.Preferably, the alkalizing agent is sodium hydride.Preferably, the epoxidation reagent is ring
Oxygen chloropropane.Preferably, the specific steps isolated and purified are as follows: reaction solution is added in ether, filters, is washed again with ether
It washs several times, product is dissolved into methylene chloride, is washed with distilled water by vacuum drying, and liquid separation is dry with anhydrous magnesium sulfate, takes out
Filtrate decompression is distilled after filter.
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 4), the poly- second two of the quaternized carboxyalkyl chitosan and epoxidation modification
The mass parts ratio of alcohol 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 pH value range is 10~14.
According to the above scheme, it is preferable that 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.
According to the above scheme, it is preferable that the solvent B is distilled water, tetrahydrofuran, isopropanol, sodium hydroxide solution, N, N-
Dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, acetic acid, methanol it is one or more.
According to the above scheme, it is preferable that in each step, the lye is sodium hydroxide, potassium hydroxide, sodium carbonate, carbon
One of sour 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 quasi-oil desalination demulsifier, includes the following steps:
(1) epoxidation modification of poly glycol monomethyl ether terminal hydroxy group: taking polyethylene glycol monomethyl ether (Mn=350) 1.75g
(5mmol) is dissolved in 50mL dry toluene, is added 50mL tetrahydrofuran and 0.18g (7.5mmol) hydrogenation sodium reagent, is warming up to
25 DEG C, react 2h.1.6mL (20mmol) epoxychloropropane is slowly dropped in reaction solution, 40 DEG C of temperature, reacts 6h.Reaction
Liquid is added in 200mL ether, filters, and is relaundered several times with ether, and product is dissolved into 200mL methylene chloride by vacuum drying
In, it is washed with distilled water liquid separation three times, dry with anhydrous magnesium sulfate, filtrate decompression is distilled after suction filtration, and freeze-drying obtains epoxy
Polyethylene 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 the dissolution of 30mL water is added, 5mL 0.04mol/L potassium hydroxide solution is added after dissolution, keeps
In nitrogen environment, stirring is warming up to 80 DEG C for reaction, and 0.7g epoxidation poly glycol monomethyl ether (Mn=350) is dissolved in 10mL water
In, it is added dropwise to complete in 10min, reacts 30h.It is dialysed 3 days with bag filter, Liquid Residue is freeze-dried poly- up to target product-in bag
The quaternized carboxymethyl chitosan of glycol monoethyl ether grafting is demulsifier 1.
Embodiment 2
A kind of preparation of chitosan quasi-oil desalination demulsifier, includes the following steps:
(1) epoxidation modification of poly glycol monomethyl ether terminal hydroxy group: taking polyethylene glycol monomethyl ether (Mn=750) 3.75g
(5mmol) is dissolved in 50mL dry toluene, is added 50mL tetrahydrofuran and 0.24g (10mmol) hydrogenation sodium reagent, is warming up to
20 DEG C, react 4h.2.4mL (30mmol) epoxychloropropane is slowly dropped in reaction solution, 35 DEG C of temperature, reacts 10h.Reaction
Liquid is added in 200mL ether, filters, and is relaundered several times with ether, and product is dissolved into 200mL methylene chloride by vacuum drying
In, it is washed with distilled water liquid separation three times, dry with anhydrous magnesium sulfate, filtrate decompression is distilled after suction filtration, and freeze-drying obtains epoxy
Polyethylene 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 the dissolution of 30mL n,N-Dimethylformamide is added, 5mL 0.04mol/L hydrogen is added after dissolution
Potassium oxide solution keeps reaction in nitrogen environment, and stirring is warming up to 80 DEG C, by 1.5g epoxidation poly glycol monomethyl ether (Mn
=750) it is dissolved in 10mL n,N-Dimethylformamide, is added dropwise to complete in 10min, react 30h.It is dialysed 3 days with bag filter, bag
Interior Liquid Residue is freeze-dried up to the quaternized carboxyetbyl chitosan of target product-poly glycol monomethyl ether grafting, is demulsifier
2。
Embodiment 3
A kind of preparation of chitosan quasi-oil desalination demulsifier, includes the following steps:
(1) epoxidation modification of poly glycol monomethyl ether terminal hydroxy group: taking polyethylene glycol monomethyl ether (Mn=1000) 5g
(5mmol) is dissolved in 50mL dry toluene, is added 50mL tetrahydrofuran and 0.36g (15mmol) hydrogenation sodium reagent, is warming up to
30 DEG C, react 2h.3.2mL (40mmol) epoxychloropropane is slowly dropped in reaction solution, 30 DEG C of temperature, reacts 16h.Reaction
Liquid is added in 200mL ether, filters, and is relaundered several times with ether, and product is dissolved into 200mL methylene chloride by vacuum drying
In, it is washed with distilled water liquid separation three times, dry with anhydrous magnesium sulfate, filtrate decompression is distilled after suction filtration, and freeze-drying obtains epoxy
Polyethylene 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, and the dissolution of 30mL dimethyl sulfoxide is added, and it is molten that 5mL 0.04mol/L potassium hydroxide is added after dissolution
Liquid keeps reaction in nitrogen environment, and stirring is warming up to 80 DEG C, and 1g epoxidation poly glycol monomethyl ether (Mn=1000) is dissolved in
It in 10mL dimethyl sulfoxide, is added dropwise to complete in 10min, reacts 40h.It is dialysed 4 days with bag filter, Liquid Residue is freeze-dried in bag to obtain the final product
The quaternized carboxylic propyl chitosan of target product-poly glycol monomethyl ether grafting, is demulsifier 3.
Embodiment 4
A kind of preparation of chitosan quasi-oil desalination demulsifier, includes the following steps:
(1) epoxidation modification of poly glycol monomethyl ether terminal hydroxy group: taking polyethylene glycol monomethyl ether (Mn=5000) 5g
(1mmol) is dissolved in 50mL dry toluene, adds 50mL tetrahydrofuran and 0.036g (1.5mmol) hydrogenation sodium reagent, heating
To 25 DEG C, 4h is reacted.0.37mL (4mmol) epoxychloropropane is slowly dropped in reaction solution, 40 DEG C of temperature, reacts 6h.Instead
It answers liquid to be added in 200mL ether, filters, relaundered several times with ether, product is dissolved into 200mL dichloromethane by vacuum drying
In alkane, it is washed with distilled water liquid separation three times, dry with anhydrous magnesium sulfate, filtrate decompression is distilled after suction filtration, and freeze-drying obtains ring
Aoxidize poly 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, adjusts 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 sulfoxide, is added drop-wise in reaction system by constant pressure funnel, is heated up 80 DEG C,
React 8h.After the reaction was completed, reaction solution is dialysed 3~5 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: take the quaternized carboxylic nonyl shell of 1.05g poly-
Sugar is placed in 250mL three-necked flask, and the dissolution of 30mL water is added, 5mL 0.04mol/L potassium hydroxide solution is added after dissolution, keeps
In nitrogen environment, stirring is warming up to 80 DEG C for reaction, and 5g epoxidation poly glycol monomethyl ether (Mn=5000) is dissolved in 10mL water
In, it is added dropwise to complete in 10min, reacts 40h.It is dialysed 4 days with bag filter, Liquid Residue is freeze-dried poly- up to target product-in bag
The quaternized carboxylic nonyl chitosan of glycol monoethyl ether grafting 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
According to a kind of shell made from the method for embodiment 1 in the bulletin text of Chinese patent application CN201310289037.6
Glycans crude oil desalting demulsifier 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 60 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
Breaking emulsion and dewatering experiment effect under the conditions of optium concentration and temperature 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 chitosan quasi-oil desalination demulsifier, which comprises the following steps:
1) poly glycol monomethyl ether terminal hydroxy group progress epoxidation is obtained into epoxidation 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 after solvent A again and 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: quaternary ammonium N prepared by step (3),
Lye adjusting pH value of solution is added after being dissolved in solvent B in O- carboxyalkyl chitosan, is warming up to 80~100 DEG C, keeps reaction in indifferent gas
Reaction system is added drop-wise in body environment, then after epoxidation modification poly glycol monomethyl ether made from step 1) is dissolved in solvent B
In, 24~48h of isothermal reaction, separating-purifying, be freeze-dried poly glycol monomethyl ether grafting quaternary ammonium N, O- carboxyalkyl shell are poly-
Sugar.
2. the preparation method of chitosan quasi-oil desalination demulsifier according to claim 1, which is characterized in that in step 1)
The specific steps of the epoxidation modification are as follows: 1 molar part poly glycol monomethyl ether is dissolved in solvent C, adds appropriate solvent D
With 1~4 molar part alkalizing agent, 20~30 DEG C are warming up to, 2~6h is reacted, 1~10 molar part epoxidation reagent is slowly added dropwise
Into reaction solution, 20~40 DEG C are warming up to, reacts 6-20h, for reaction solution after isolating and purifying, freeze-drying obtains the poly- second of epoxidation
Glycol monomethyl ether；Wherein, the number average molecular weight of the poly glycol monomethyl ether be 350,500,750,1000,1900 or
5000。
3. the preparation method of chitosan quasi-oil desalination demulsifier according to claim 2, which is characterized in that
The solvent C is dry toluene；
The solvent D is tetrahydrofuran, ethyl alcohol, dimethyl sulfoxide, methylene chloride, n,N-Dimethylformamide and N, N- dimethyl second
One of amide is a variety of；
The alkalizing agent is sodium hydride；
The epoxidation reagent is epoxychloropropane.
4. the preparation method of chitosan quasi-oil desalination demulsifier according to claim 1, which is characterized in that
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；
The solvent B is distilled water, tetrahydrofuran, isopropanol, sodium hydroxide solution, n,N-Dimethylformamide, N, N- diformazan
Yl acetamide, dimethyl sulfoxide, acetic acid, methanol it is one or more.
5. the preparation method of chitosan quasi-oil desalination demulsifier according to claim 1, which is characterized in that step 2)
In, the N, the mass parts ratio of N- dimethyl alkylamine and epoxychloropropane is 1.93~2.97:3.7.
6. the preparation method of chitosan quasi-oil desalination demulsifier according to claim 1, which is characterized in that step 3)
In, the preparation method of the N, O- carboxyalkyl chitosan are:
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。
7. the preparation method of chitosan quasi-oil desalination demulsifier according to claim 1, which is characterized in that step 3)
In, the N, the mass parts ratio of O- carboxyalkyl chitosan and glycidyl dimethyl alkyl ammomium chloride is 3.21:1.93
~7.7.
8. the preparation method of chitosan quasi-oil desalination demulsifier according to claim 1, which is characterized in that step 3)
In, by N, after O- carboxyalkyl chitosan dissolve using solvent A and used lye adjusting solution ph, then the solution is warming up to
45~50 DEG C, isothermal reaction 1h.
9. the preparation method of chitosan quasi-oil desalination demulsifier according to claim 1, which is characterized in that step 3)
In, the pH value range is 8~10；PH value range described in step 4) is 10~14.
10. the preparation method of chitosan quasi-oil desalination demulsifier according to claim 1, which is characterized in that step 4)
In, the quaternary ammonium N, the mass parts ratio of the poly glycol monomethyl ether of O- carboxyalkyl chitosan and epoxidation modification are as follows: 0.47
~1.05:0.35~5.
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