CN106279706B - A kind of preparation method of polyether grafting chitosan derivatives crude oil desalting demulsifier - Google Patents
A kind of preparation method of polyether grafting chitosan derivatives crude oil desalting demulsifier Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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Abstract
The present invention relates to a kind of preparation methods of polyether grafting chitosan derivatives crude oil desalting demulsifier.Specific step is as follows: (1) carrying out poly glycol monomethyl ether aldehyde grouping modified；(2) glycidyl dimethyl alkyl ammomium chloride is prepared；(3) quaternized carboxyalkyl chitosan is prepared；(4) by aldehyde grouping modified poly glycol monomethyl ether and quaternized carboxyalkyl chitosan reaction, polyether grafting chitosan derivatives crude oil desalting demulsifier is obtained.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 polyether grafting chitosan derivatives crude oil desalting demulsifier, belong to petroleum
Work 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
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 polyether grafting chitosan for above-mentioned problems of the prior art and spread out
The preparation method of bio-crude oil desalination demulsifier, obtain it is a series of be appropriate to heterogeneity crude oil, and can be while demulsification
Slough the high-efficient demulsifier of oil-soluble salt.
To achieve the above object, present invention provide the technical scheme that
A kind of preparation method of polyether grafting chitosan derivatives crude oil desalting demulsifier, which is characterized in that including following
Step:
1) poly glycol monomethyl ether terminal hydroxy group progress hydroformylation is obtained into hydroformylation modified poly (ethylene 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, then the resulting glycidyl dimethyl alkyl ammomium chloride of step 2) is dissolved in solvent A, it is added dropwise to reactant
System, 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 of solid product
Chitosan；
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, then is added dropwise after hydroformylation modified poly (ethylene glycol) monomethyl ether made from step 1) is dissolved using solvent B
Into reaction system, appropriate alkaline liquor is added and adjusts solution ph in a certain range, adds a certain amount of reducing agent, is warming up to
50~80 DEG C, 6~12h of isothermal reaction, reaction solution after isolating and purifying, be freeze-dried final product poly glycol monomethyl ether connects
The quaternized carboxyalkyl chitosan of branch.
According to the above scheme, it is preferable that aldehyde grouping modified specific steps described in step 1) are as follows: by the poly- second two of 1 molar part
Alcohol monomethyl ether is dissolved in a certain amount of solvent C, keeps reaction in inert gas environment, room temperature is added 5 under the conditions of being stirred continuously
~20 parts of aldehyde radical reagents, are warming up to 15~35 DEG C, and 5~15h of isothermal reaction after isolating and purifying reaction solution, is dried in vacuo
To hydroformylation poly glycol monomethyl ether；Wherein, the number average molecular weight of the poly glycol monomethyl ether be 350,500,750,1000,
1900 or 5000.Preferably, the solvent C is one of methylene chloride, chloroform, dimethyl sulfoxide, ether or a variety of.It is excellent
Selection of land, the aldehyde radical reagent are acetic anhydride.Preferably, inert gas environment is nitrogen or argon gas.Preferably, the separation is pure
It turns to and reaction solution is added in anhydrous ether, obtained precipitating chloroform, which dissolves, recrystallizes with diethyl ether solution again and repeat this step
It is rapid primary.
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), 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 pH value range is 8~10.
According to the above scheme, it is preferable that in step 4), the pH value range is 5~7.
According to the above scheme, it is preferable that in step 4), the quaternized carboxyalkyl chitosan, hydroformylation modified poly (ethylene glycol)
The mass parts ratio of monomethyl ether and reducing agent are as follows: (0.47~1.05): (0.35~5): (0.08~0.183).
According to the above scheme, it is preferable that in step 4), the reducing agent includes but is not limited to sodium borohydride or cyano hydroboration
Sodium.
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, isopropanol, aqueous sodium carbonate, N, N- dimethyl methyl
One of amide, DMAC N,N' dimethyl acetamide, acetic acid, ethyl alcohol, methanol, acetone, saturated ammonium sulfate solution are a variety of.
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 invention has 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
The quaternized carboxyalkyl chitosan for the poly glycol monomethyl ether grafting that the method for the present invention obtains 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) in the present invention polyether grafting chitosan derivatives crude oil desalting demulsifier preparation method, it is different selection can be passed through
The carboxyalkyl acid sodium of carbon chain lengths, N, N- dimethyl alkylamine, polyethers perhaps change reaction raw materials amount ratio or change anti-
The conditions such as reaction temperature and the time of system are answered, to change demulsifier molecular structure such as molecular weight, degree of substitution, hydrophobic chain segment length
Aggregated structure etc. is spent, and then regulates and controls the desalting and dewatering effect of the high-efficient demulsifier of synthesis, (difference produces to be suitable for heterogeneity
Ground, 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 polyether grafting chitosan derivatives crude oil desalting demulsifier, the specific steps are as follows:
(1) poly glycol monomethyl ether terminal hydroxy group is aldehyde grouping modified: taking 1.75g (5mmol) poly glycol monomethyl ether (Mn=
350) it is dissolved in the mixed solution of 30mL anhydrous dimethyl sulfoxide and 2mL chloroform, keeps reaction in nitrogen environment, at room temperature constantly
5.1mL (50mmol) solution of acetic anhydride is added under stirring condition, is heated to 15 DEG C, isothermal reaction 5h.It after the reaction was completed will reaction
Liquid is added in 400mL anhydrous ether, and obtained precipitating chloroform, which dissolves, (repeats this step 1 with diethyl ether solution recrystallization again
It is secondary), then be dried in vacuo obtain hydroformylation poly glycol monomethyl ether for 24 hours at room temperature.
(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, 0.4g aldehyde radical polyethylene glycol monomethyl ether (Mn=350) is dissolved in
In 10mL water, appropriate potassium carbonate is added and adjusts solution PH=6, adds 0.08g sodium borohydride, is added dropwise to complete in 10min, stirs
50 DEG C are warming up to, isothermal reaction 6h.Reaction solution is poured into saturated ammonium sulfate solution and is precipitated, is filtered, is used after filtrate freeze-drying
Ethyl alcohol and acetone washing are dried in vacuo afterwards several times up to the quaternized carboxymethyl shell of target product-poly glycol monomethyl ether grafting
Glycan is demulsifier 1.
Embodiment 2
A kind of preparation of polyether grafting chitosan derivatives crude oil desalting demulsifier, the specific steps are as follows:
(1) poly glycol monomethyl ether terminal hydroxy group is aldehyde grouping modified: taking polyethylene glycol monomethyl ether (Mn=750) 3.75g
(5mmol) is dissolved in the mixed solution of 30mL anhydrous dimethyl sulfoxide and 2mL chloroform, keeps reaction in nitrogen environment, at room temperature
5.1mL (50mmol) solution of acetic anhydride is added under the conditions of being stirred continuously, is heated to 20 DEG C, isothermal reaction 7h.After the reaction was completed will
Reaction solution is added in 400mL anhydrous ether, and obtained precipitating chloroform, which dissolves, (repeats this step with diethyl ether solution recrystallization again
Once), then at room temperature it is dried in vacuo and obtains hydroformylation poly glycol monomethyl ether for 24 hours.
(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 water is added, 0.8g aldehyde radical polyethylene glycol monomethyl ether (Mn=750) is dissolved in
In 10mL water, appropriate potassium carbonate is added and adjusts solution PH=6, adds 0.16g sodium borohydride, is added dropwise to complete in 10min, stirs
65 DEG C are warming up to, isothermal reaction 7h.Reaction solution is poured into saturated ammonium sulfate solution and is precipitated, is filtered, is used after filtrate freeze-drying
Ethyl alcohol and acetone washing are dried in vacuo afterwards several times up to the quaternized carboxyethyl shell of target product-poly glycol monomethyl ether grafting
Glycan is demulsifier 2.
Embodiment 3
A kind of preparation of polyether grafting chitosan derivatives crude oil desalting demulsifier, the specific steps are as follows:
(1) poly glycol monomethyl ether terminal hydroxy group is aldehyde grouping modified: taking polyethylene glycol monomethyl ether (Mn=1000) 5g
(5mmol) is dissolved in the mixed solution of 30mL anhydrous dimethyl sulfoxide and 2mL chloroform, keeps reaction in nitrogen environment, at room temperature
5.1mL (50mmol) solution of acetic anhydride is added under the conditions of being stirred continuously, is warming up to 30 DEG C, the isothermal reaction time is 9h.It has reacted
Reaction solution is added in 400mL anhydrous ether after, obtained precipitating chloroform dissolves (to be repeated with diethyl ether solution recrystallization again
This step is primary), then be dried in vacuo obtain hydroformylation poly glycol monomethyl ether for 24 hours at room temperature.
(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 water is added, 1.1g aldehyde radical polyethylene glycol monomethyl ether (Mn=1000) is dissolved in
In 10mL water, appropriate potassium carbonate is added and adjusts solution PH=6, adds 0.183g sodium borohydride, is added dropwise to complete, stirs in 10min
It mixes and is warming up to 80 DEG C, isothermal reaction 8h.Reaction solution is poured into saturated ammonium sulfate solution and is precipitated, is filtered, after filtrate freeze-drying
It is dried in vacuo afterwards several times with ethyl alcohol and acetone washing up to the quaternized carboxylic propyl of target product-poly glycol monomethyl ether grafting
Chitosan is demulsifier 3.
Embodiment 4
A kind of preparation of polyether grafting chitosan derivatives crude oil desalting demulsifier, the specific steps are as follows:
(1) poly glycol monomethyl ether terminal hydroxy group is aldehyde grouping modified: taking polyethylene glycol monomethyl ether (Mn=5000) 5g
(1mmol) is dissolved in the mixed solution of 30mL anhydrous dimethyl sulfoxide and chloroform 2mL, keeps reaction in nitrogen environment, at room temperature
1.1mL (10mmol) solution of acetic anhydride is added under the conditions of being stirred continuously, is warming up to 35 DEG C, isothermal reaction 15h.After the reaction was completed will
Reaction solution is added in 400mL anhydrous ether, and obtained precipitating chloroform, which dissolves, (repeats this step with diethyl ether solution recrystallization again
Once), then at room temperature it is dried in vacuo and obtains hydroformylation poly glycol monomethyl ether for 24 hours.
(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 the dissolution of 30mL water is added, 5g aldehyde radical polyethylene glycol monomethyl ether (Mn=5000) is dissolved in
In 10mL water, appropriate potassium carbonate is added and adjusts solution PH=6, adds 0.183g sodium borohydride, is added dropwise to complete, stirs in 10min
It mixes and is warming up to 65 DEG C, isothermal reaction 8h.Reaction solution is poured into saturated ammonium sulfate solution and is precipitated, is filtered, after filtrate freeze-drying
It is dried in vacuo afterwards several times with ethyl alcohol and acetone washing up to the quaternized carboxylic nonyl of target product-poly glycol monomethyl ether grafting
Chitosan 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 more according to one kind made from the method for embodiment 1 in the bulletin text of Chinese patent application CN201310289037.6
The crude oil demulsifier of carbohydrate 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 70ppm, 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
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. a kind of preparation method of polyether grafting chitosan derivatives crude oil desalting demulsifier, which is characterized in that including following step
It is rapid:
1) poly glycol monomethyl ether terminal hydroxy group is subjected to aldehyde grouping modified hydroformylation modified poly (ethylene 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
Solution ph is saved, then the resulting glycidyl dimethyl alkyl ammomium chloride of step 2) is dissolved in after solvent A and is added dropwise to reaction
System, is warming up to 60~80 DEG C, after reaction 8~for 24 hours, reaction solution is dialysed, is freeze-dried, obtains 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), O-
Carboxyalkyl chitosan is dissolved in solvent B, then by hydroformylation modified poly (ethylene glycol) monomethyl ether made from step 1) using solvent B dissolution after
It is added drop-wise in reaction system, appropriate alkaline liquor is added and adjusts solution ph in a certain range, adds a certain amount of reducing agent, rises
For temperature to 50~80 DEG C, 6~12h of isothermal reaction, reaction solution is freeze-dried to obtain poly glycol monomethyl ether grafting after isolating and purifying
Quaternary ammonium N, O- carboxyalkyl chitosan.
2. the preparation method of polyether grafting chitosan derivatives crude oil desalting demulsifier according to claim 1, feature
It is the modified specific steps of the step 1) hydroformylation are as follows: 1 part of poly glycol monomethyl ether of molar part is dissolved in solvent C, is kept
In inert gas environment, 5~20 molar part aldehyde radical reagents are added under the conditions of being stirred continuously in room temperature for reaction, are warming up to 15~35
DEG C, 5~15h of isothermal reaction, after reaction solution is isolated and purified, vacuum drying obtains hydroformylation poly glycol monomethyl ether；Wherein, described
The number average molecular weight of poly glycol monomethyl ether is 350,500,750,1000,1900 or 5000.
3. the preparation method of polyether grafting chitosan derivatives crude oil desalting demulsifier according to claim 2, feature
It is:
The solvent C is one of methylene chloride, chloroform, dimethyl sulfoxide, ether or a variety of；
The aldehyde radical reagent is acetic anhydride；
The inert gas is nitrogen or argon gas；
The precipitating obtained for reaction solution to be added in anhydrous ether that isolates and purifies is dissolved with chloroform again with diethyl ether solution weight
It crystallizes and to repeat this step primary.
4. the preparation method of polyether grafting chitosan derivatives crude oil desalting demulsifier according to claim 1, feature
It is, in step 2), the N, the mass parts ratio of N- dimethyl alkylamine and epoxychloropropane is 1.93~2.97:3.7.
5. the preparation method of polyether grafting chitosan derivatives crude oil desalting demulsifier according to claim 1, feature
It is N described in step 3), 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。
6. the preparation method of polyether grafting chitosan derivatives crude oil desalting demulsifier according to claim 1, feature
It is, in step 3), the N, the mass parts ratio of O- carboxyalkyl chitosan and glycidyl dimethyl alkyl ammomium chloride
For 3.21:1.93~7.7.
7. the preparation method of polyether grafting chitosan derivatives crude oil desalting demulsifier according to claim 1, feature
It is, in step 3), the pH value range is 8~10；In step 4), the pH value range is 5~7.
8. the preparation method of polyether grafting chitosan derivatives crude oil desalting demulsifier according to claim 1, feature
It is, in step 3), by N, after O- carboxyalkyl chitosan is dissolved using solvent A and lye is used to adjust solution ph, then incites somebody to action
The solution is warming up to 45~50 DEG C, isothermal reaction 1h.
9. the preparation method of polyether grafting chitosan derivatives crude oil desalting demulsifier according to claim 1, feature
It is, in step 4), the quaternary ammonium N, O- carboxyalkyl chitosan, aldehyde grouping modified poly glycol monomethyl ether and reducing agent
Mass parts ratio are as follows: (0.47~1.05): (0.35~5): (0.08~0.183).
10. the preparation method of polyether grafting chitosan derivatives crude oil desalting demulsifier according to claim 1, feature
It is,
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 be distilled water, isopropanol, aqueous sodium carbonate, n,N-Dimethylformamide, n,N-dimethylacetamide,
One of acetic acid, ethyl alcohol, methanol, acetone, saturated ammonium sulfate solution are a variety of；
Reducing agent described in step 4) includes but is not limited to sodium borohydride or sodium cyanoborohydride.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103320158A (en) * | 2013-07-10 | 2013-09-25 | 武汉工程大学 | Natural polysaccharide macromolecule-modified crude oil demulsifier |
-
2016
- 2016-08-09 CN CN201610644993.5A patent/CN106279706B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103320158A (en) * | 2013-07-10 | 2013-09-25 | 武汉工程大学 | Natural polysaccharide macromolecule-modified crude oil demulsifier |
Non-Patent Citations (2)
| Title |
|---|
| 多糖类原油破乳剂的合成及其性能研究;王磊;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20150315(第3期);正文第27、36-37页 |
| 多糖类原油破乳剂的合成及其破乳性能;王存文 等;《武汉工程大学学报》;20131231;第35卷(第12期);第1-5页 |
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