CN108865233A - A kind of novel crude oil demulsifier and preparation method thereof - Google Patents
A kind of novel crude oil demulsifier and preparation method thereof Download PDFInfo
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- CN108865233A CN108865233A CN201810805783.9A CN201810805783A CN108865233A CN 108865233 A CN108865233 A CN 108865233A CN 201810805783 A CN201810805783 A CN 201810805783A CN 108865233 A CN108865233 A CN 108865233A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1033—Oil well production fluids
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Abstract
The present invention relates to a kind of novel crude oil demulsifiers and preparation method thereof.The general structure of the novel crude oil demulsifier is shown in formula I, and preparation method is as follows：1) be acylated modified N- acylation chitosan to chitosan；2) modified to N- acylation chitosan progress carboxylation alkylation that N- is acylated carboxyalkyl chitosan；3) epoxidation modification is carried out to the terminal hydroxy group of poly glycol monomethyl ether and obtains epoxidation poly glycol monomethyl ether；4) modified poly (ethylene glycol) monomethyl ether and the acylated carboxyalkyl chitosan reaction of N- obtain the acylated carboxyalkyl chitosan of N- of target product poly glycol monomethyl ether grafting.The present invention has many advantages, such as wide source, natural, nontoxic, good biocompatibility, degradable using chitosan class natural polymer as raw material.Carboxyalkyl, acyl group and polyether lateral chain are introduced in chitosan molecule chain, by controlling position and the degree of substitution of each substituent group, obtain a series of high-efficient demulsifiers for being appropriate to oil-in-water (O/W) type emulsion.
Description
Technical field
The present invention relates to a kind of novel crude oil demulsifiers and preparation method thereof, belong to petrochemical industry.
Background technique
In oil extraction process, with the oil recoveries work such as steam flooding, surfactant, polymer and ternary composite oil-displacing
The implementation of skill technology, emulsion of crude oil moisture content increase, and stability enhances, and crude oil demulsification difficulty increases.The formation meeting of emulsion
A series of serious harm are brought to the exploitation of petroleum, transport and processing.Emulsification, which occurs, for crude oil and water can make crude oil production
Difficulty increases；It will increase the load and freight of pump when with pipeline or tank car transport wet crude.Therefore, in carried of crude oil
It is very necessary with desalting and dewatering is carried out to crude oil emulsion before processing.
Emulsion is sufficiently complex dispersion, mainly based on Water-In-Oil (W/O) type, with answering for oil recovery new technology
With having gradually appeared oil-in-water (O/W) type emulsion in Produced Liquid.Common breaking method have flotation, chemical coagulation, chemistry and
Electrochemical techniques, chemical demulsification, film point and biotechnology etc., most widely used or chemical demulsification method.Chemical demulsification method
Required demulsifier has the history of last 100 years, experienced update generation upon generation of, the effect of demulsifier is become better and better, and dosage is more next
It is fewer.But as emulsion becomes increasingly complex, the specificity of demulsifier is also increasingly stronger.Currently, the crude oil that China oil field uses
Demulsifier is based on block polymer, and the trend that oriented super high molecular weight direction is developed.Polysaccharide natural polymer source is wide
It is general, with fabulous biocompatibility and environment friendly, and molecular weight is big, active hydrogen is more, has branched structure and unique
Rheologic behavio(u)r, the area occupied by oil-water interfaces is big, has preferable temperature tolerance, higher interfacial activity, and to environment
It is pollution-free, it is the splendid candidate target of demulsifier initiator.Guo Donghong etc. makees initiator with xanthan gum or melon bean gum, with ring
Oxidative ethane, propylene oxide addition have synthesized the polysaccharide natural polymer demulsifier with polyethers branched structure, and have been demulsified to it
Performance has carried out simple evaluation.In colas 90% water can be effectively removed in the discovery ethyl cellulose such as Xu, and
Systematically have studied its Mechanismic.Wang Lei etc., for initiator, has synthesized five kinds of polysaccharide crude oil demulsifiers, and right with polysaccharide etc.
Its demulsification performance has made certain evaluation.Fan etc. has synthesized a series of chitosan crude oil demulsifiers, is 60 DEG C of items in demulsification temperature
Under part, there is certain breaking emulsion and dewatering effect to water-in-oil type (W/O) crude oil emulsion, and inquired into its Mechanismic.
Chitosan is the natural polymer that yield is only second to cellulose in nature, is widely present arthropods class (spider
Class, shell-fish) wing and shell in, exist in the cell wall of fungi and algae, with fabulous biocompatibility and
Environment friendly.Compared with the polysaccharide such as xanthan gum and cellulose family, chitosan contains more active active amino, it is easier to connect
Branch is modified.Carboxymethyl chitosan is can be obtained into chitosan progress carboxy methylation, due to the introducing of hydrophilic groups, is greatly changed
The dissolubility of chitosan is become；Quaternised modified to carboxymethyl chitosan progress, existing carboxyl has season again in available molecule
The Amphiphatic high polymer electrolyte of ammonium salt groups.Chinese patent CN 201310289037.6 describes a kind of polysaccharide-modified crude oil
Demulsifier.Using polysaccharide as initiator, and it is carried out quaternised modified, polyether graft modified, obtains a kind of polysaccharide-modified original
Oily demulsifier.Chinese patent CN 201610644945.6 describes a kind of preparation side of polyelectrolyte type crude oil desalting demulsifier
Method.By glycidyl dimethyl alkyl ammomium chloride and it is amination modified after polyether grafting to carboxymethyl chitosan on, obtain
To a kind of polyelectrolyte type crude oil desalting demulsifier.Chinese patent CN201610644992.0 is by glycidyl dimethyl alkyl
On ammonium chloride and the modified polyether grafting to carboxymethyl chitosan of isocyanation esterification, it is de- to obtain a kind of new and effective crude oil
Salt demulsifier.Chinese patent CN201610644943.7 changes glycidyl dimethyl alkyl ammomium chloride and acroleic acid esterification
On polyether grafting to carboxymethyl chitosan after property, a kind of crude oil desalting demulsifier of comb polymer is obtained.Chinese patent
CN201610644993.5 by glycidyl dimethyl alkyl ammomium chloride and it is aldehyde grouping modified after polyether grafting to carboxylic first
On base enclosure glycan, a kind of chitosan derivatives crude oil desalting demulsifier of polyether grafting is obtained.Chinese patent
CN201610645442.0 arrives glycidyl dimethyl alkyl ammomium chloride and the modified polyether grafting of p-nitrophenyl ester
On carboxymethyl chitosan, a kind of efficient crude oil desalting demulsifier is obtained.Chinese patent CN201610645444.X will shrink sweet
On polyether grafting to carboxymethyl chitosan after oleyl dimethyl alkyl ammomium chloride and epoxidation modification, a kind of chitosan is obtained
Quasi-oil desalination demulsifier.Chinese patent CN201610645497.1 is by glycidyl dimethyl alkyl ammomium chloride and halogenation
On modified polyether grafting to carboxymethyl chitosan, a kind of crude oil desalting demulsification of chitosan class natural macromolecule modification is obtained
Agent.Chinese patent CN201610648933.0 connects the polyethers after glycidyl dimethyl alkyl ammomium chloride and esterification modification
On branch to carboxymethyl chitosan, a kind of double ion type crude oil desalting demulsifier is obtained.The above type demulsifier is in addition to polysaccharide
It, can be with while demulsification outside many advantages, such as class demulsifier is from a wealth of sources, natural, nontoxic, sustainable, safety in utilization is good
Remove crude oil emulsion oil-soluble salt.But these types of chitosan class demulsifier is primarily directed to Water-In-Oil (W/O) type original
Oil emulsion.
With a large amount of uses of oil recovery new technology, while improving oil recovery factor, but also oil-in-water (O/W) type is newborn
Shape liquid proportional is increasing, and stability is more and more stronger.Composition contained by oil-in-water (O/W) type emulsion is more complicated, generally
Including sump oil, scale, organic substance, corrosive gas, mud and clay, surfactant and cosurfactant etc..Due to
The presence of these substances, can greatly reduce the tension of oil-water interfaces and the Zeta-potential of oil droplets, and institute in emulsion
The viscosity of water can be improved in the high polymer contained again, so as to form highly stable oil-in-water (O/W) type lotion, this emulsion
Break milk separation it is very difficult.
Currently, the domestic demulsifier for oil-in-water (O/W) type emulsion only has CW-01, PDM-1, BH-1, RD-1 etc. several
Kind.These demulsifier environment friendly are poor, be easy to cause irreversible secondary pollution；In addition, each crude oil Produced Liquid
All there is more or less differences for ingredient and property, and there is no the demulsifiers for being capable of handling all types crude oil Produced Liquid.Cause
This, developing, there is oil-in-water (O/W) the type demulsifier of novel environmental close friend to solve due to oil recovery new technology and bring problem,
Have become important and urgent need to resolve a project of oil field later development.
Summary of the invention
The present invention proposes a kind of novel crude oil demulsifier and its preparation side for above-mentioned problems of the prior art
Method.The demulsifier using chitosan class natural polymer as raw material, in chitosan molecule chain introduce alkyl, acyl group and
Polyether lateral chain, obtained demulsifier can realize efficiently demulsification for oil-in-water (O/W) type crude oil emulsion.The system of the demulsifier
Preparation Method have extensive raw material sources, natural, nontoxic, good biocompatibility, it is degradable many advantages, such as.
To achieve the above object, technical solution provided by the invention is as follows：
A kind of novel crude oil demulsifier, which is characterized in that there is general structure shown in following formula (I)s：
It is specific as follows the present invention also provides a kind of preparation method of novel crude oil demulsifier：
A kind of preparation method of novel crude oil demulsifier, which is characterized in that include the following steps：
1) amino on chitosan is subjected to acylation modification and obtains N- acylation chitosan, the specific steps are：
Chitosan is dissolved in aqueous solutions of organic acids, Organic Alcohol dilution is added, under agitation by the chitosan
0.5 times of addition acid anhydrides of the amount of the substance of amino places 24~48h under room temperature, and precipitating reagent is added, sediment is washed,
Freeze-drying, obtains N- acylation chitosan；Preferably, the volumetric usage of the Organic Alcohol accounts for 80% of whole system or more.
(acylation reaction carries out in the homogeneous system that Organic Alcohol, organic acid and water form, and the content of Organic Alcohol is up to 80% in system.
Just because of the Competition of organic alcoholic extract hydroxyl group, acylation reaction is preferentially carried out in the amino of saccharide ring, so that it is excellent to have this system
Good selectivity, only acylation reaction occurs for the amino at C2.)
2) modified to N- acylation chitosan progress carboxylation alkylation that N- is acylated carboxyalkyl chitosan, the specific steps are：
N- acylation chitosan made from step 1) is dissolved in or is swollen in solvent A, 1~2h of lye alkalization is added；Alkalization
After the completion, carboxylated reagent chloro alkyl acid sodium is added in reaction solution, is warming up to 50~100 DEG C after adding, reaction 2~
7h, it is neutrality that acid solution, which is added, and adjusts the pH of reaction solution；Reaction product is filtered, Washing of Filter Cake dialysis, freeze-drying obtains N-
Acylated carboxyalkyl chitosan；Wherein it is preferred to which the carbon chain lengths of the chloro alkyl acid sodium are C2-C18。
3) epoxidation modification is carried out to the terminal hydroxy group of poly glycol monomethyl ether and obtains epoxidation poly glycol monomethyl ether, it is specific
Steps are as follows：
1 molfraction poly glycol monomethyl ether is dissolved in solvent B at room temperature, adds appropriate solvent C and 1~5 mole
Part alkalizing agent, is warming up to 20~40 DEG C, reacts 3~8h, then 2.5~10 molfraction epoxidation reagents are slowly dropped to instead
It answers in liquid, is warming up to 20~40 DEG C of 3~20h of reaction, reaction solution is isolated and purified, is freeze-dried, and obtains epoxidation polyethyleneglycol
Methyl ether；Wherein, the number average molecular weight of the poly glycol monomethyl ether is between 350~5000.
4) epoxidation poly glycol monomethyl ether and the acylated carboxyalkyl chitosan reaction of N-, specific step is as follows：
The acylated carboxyalkyl chitosan of the N- being prepared in step 2) is dissolved in or is swollen in solvent D, lye tune is added
The pH value for saving solution in a certain range, the epoxidation poly glycol monomethyl ether being prepared is dissolved in after solvent B and is added drop-wise to instead
It answers in system, stirring heating, temperature is 80~120 DEG C, isothermal reaction 12~for 24 hours, reaction solution is isolated and purified, freeze-drying,
Obtain the acylated carboxyalkyl chitosan of N- of the modified poly- diethanol monomethyl ether grafting of target product.
According to the above scheme, it is preferable that Organic Alcohol described in step 1) be methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol,
The carbon atom numbers such as isobutanol are one of fatty alcohol of 1-10 or a variety of；The acid anhydrides is acetic anhydride, propionic andydride, n-butyric acie
The carbon atom numbers such as acid anhydride, isobutyric anhydride, positive valeric anhydride, n-caproic anhydride, caprylic acid acid anhydride are in acid anhydrides corresponding to the fatty acid of 2-10
It is one or more；The precipitating reagent is acetone.
According to the above scheme, it is preferable that in step 2), the mass parts ratio of the N- acylation chitosan and chloro alkyl acid sodium
For (1~1.256):(4.6~15.48).
According to the above scheme, it is preferable that in step 2), N- acylation chitosan is being dissolved in or is being swollen in solvent A and is being added
During lye alkalizes, the Adding Way of the lye is a small amount of repeatedly addition；After the completion of alkalization, the carboxylated reagent
The adding manner of chloro alkyl acid sodium is a small amount of repeatedly addition.
According to the above scheme, it is preferable that in step 3), the alkalizing agent is sodium hydride or sodium hydroxide；The epoxy
Change reagent is epoxychloropropane.According to the above scheme, it is preferable that in step 4), the acylated carboxyalkyl chitosan of the N- and epoxidation
The mass parts ratio of poly glycol monomethyl ether is 0.289~0.821:0.816~10.116.
According to the above scheme, it is preferable that in step 4), the solution ph range is 9~14.
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, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, acetic acid, mixture one or more in methanol；
According to the above scheme, it is preferable that the solvent B is dry toluene.
According to the above scheme, it is preferable that the solvent C is tetrahydrofuran, ethyl alcohol, dimethyl sulfoxide, methylene chloride, N, N- diformazan
One of base formamide, DMAC N,N' dimethyl acetamide are a variety of.
According to the above scheme, it is preferable that the solvent D is distilled water, isopropanol, sodium hydroxide solution, N, N- dimethyl methyl
One of amide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, acetic acid, methanol are a variety of
Synthetic route of the invention is as follows：
1, epoxidation modification is carried out to poly glycol monomethyl ether terminal hydroxy group, modified poly glycol monomethyl ether is denoted as
MPEG-M：
2, the acylated carboxyalkyl chitosan of preparation N-, the acylated carboxyalkyl chitosan of the N- of synthesizing polyethylene glycol monomethyl ether grafting：
Compared with prior art, the present invention has the advantages that：
1) present invention has from a wealth of sources, natural, nontoxic, biological using chitosan class natural polymer as raw material
Degradability and compatibility, it is sustainable, safety in utilization is good many advantages, such as.
2) the acylated carboxyalkyl chitosan of N- of modified poly (ethylene glycol) monomethyl ether grafting prepared by the present invention is a kind of efficient
Crude oil demulsifier.The demulsifier is pectinate texture and molecular weight is big, branch is more, and the area occupied by oil-water interfaces is big, has
Higher interfacial activity.The demulsifier has stronger competitive Adsorption ability in oil-water interfaces, is easy to adsorb on oil-water interfaces
With the naturally occurring emulsifying agents such as pitch, paraffin, resin of displacement adsorbed on interfaces, can be real for oil-in-water (O/W) type crude oil emulsion
Now efficiently demulsification.The addition of the demulsifier assembles emulsion drop, forms bigger oil droplet, destroys oil-water interfacial film, in turn
Achieve the effect that the de-oiling that is demulsified, the water phase after demulsification is limpid, and oil-water interfaces are neat, and de-oiling efficiency is high.
3) method that chitosan class natural macromolecule modification crude oil demulsifier is prepared in the present invention, can be by selecting different carbon
Carboxyalkyl acid sodium, the alkyl chain of chain length, perhaps change reaction raw materials amount ratio or change reaction system reaction temperature and
The conditions such as time, thus change demulsifier molecular structure such as molecular weight, degree of substitution, hydrophobic segment length aggregated structure etc., into
And regulate and control the de-oiling effect of the high-efficient demulsifier of synthesis, to be suitable for heterogeneity (different sources, oil-containing 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
The positive bytyry carboxymethyl chitosan of N- of polyethanol monomethyl ether grafting is prepared, specific step is as follows：
(1) synthesis of N- acylation chitosan：By 2g chitosan (CS) (Mw=179.17kDa, deacetylation>95%, viscosity
100~200mPas) it is dissolved in 40mL10% acetic acid aqueous solution, 160mL methanol dilution is added, is added under agitation just
Butyric anhydride 5.9mmol is placed 260mL acetone is added afterwards for 24 hours as precipitating reagent, sediment methanol and ether at room temperature
Three times, freeze-drying obtains the positive bytyry chitosan (A of white water-soluble solid N- for each washing4CS)。
Wherein the dosage of n butanoic anhydride is 0.5 times of the amount of contained amino material in chitosan, and circular is as follows：
The sugar unit of chitosan is aminoglucose saccharide residue, and the molecular weight of this residue (sugar unit of chitosan) is 161,2g
Chitosan (deacetylation>95%) amount of institute's amino-containing material is：2g ÷ 161g/mol × 95%=0.0118mol, i.e.,
11.8mmol；The amount of so substance of n butanoic anhydride is：0.5 × 11.8mmol=5.9mmol.
(2) carboxy methylation of the positive bytyry chitosan of N-：Take 1g A4100mL is added in 250mL three-necked flask in CS
Distilled water, to be completely dissolved at room temperature, taking 10mL concentration is that 10% sodium hydroxide solution is divided into 5 parts, points 5 times, every time
Interval 5min is added in reaction solution, and alkalize 1h.After the completion of alkalization, 4.6g sodium chloroacetate is divided into 5 parts, at interval of 1min plus
Enter portion into reaction solution, 60 DEG C are warming up to after adding, reacts 2h, the pH of reaction solution is adjusted to neutrality with acetic acid.Reaction is completed
After filter, filter cake three times, is dialysed three days with acetone washing after washing, freeze-drying, obtain the positive bytyry carboxymethyl chitosan of N-
Sugar (A4CMC)。
(3) synthesis of epoxidation poly glycol monomethyl ether：Taking polyethylene glycol monomethyl ether (Mn=5000) 5g (1mmol) is dissolved in
In 50mL dry toluenes, the tetrahydrofuran of 50mL and the hydrogenation sodium reagent of 0.036g (1.5mmol) are added, is warming up to 25 DEG C,
React 4h.0.37mL (4mmol) epoxychloropropane is slowly dropped in reaction solution, 40 DEG C of temperature, reacts 6h.Reaction solution is added
It in the ether of 200mL, filters, is relaundered 3 times with ether, be dried in vacuo, product is dissolved into 200mL methylene chloride, use
Distill water washing three times, liquid separation is dry with anhydrous magnesium sulfate, and filtrate decompression is distilled after suction filtration, and it is poly- that freeze-drying obtains epoxidation
Glycol monoethyl ether；
(4) synthesis of the positive bytyry carboxymethyl chitosan of N- of poly glycol monomethyl ether grafting：Take 0.289g A4CMC
In the three-necked flask of 250mL, 50mL distilled water is added, the pH=9 of sodium hydrate regulator solution is added, takes 10.116g epoxidation
Poly glycol monomethyl ether is dissolved in 10mL dry toluene, is added drop-wise in reaction system, is stirred in 10min by constant pressure funnel
It mixes and is warming up to 110 DEG C, isothermal reaction is for 24 hours.Reaction solution is dialysed 3 days after the reaction was completed, freeze-drying obtains polyethanol monomethyl ether
The positive bytyry carboxymethyl chitosan of the N- of grafting is demulsifier 1.
Embodiment 2
The positive bytyry carboxymethyl chitosan of N- of polyethanol monomethyl ether grafting is prepared, specific step is as follows：
(1) synthesis of N- acylation chitosan：By 2g chitosan (CS) (Mw=179.17kDa, deacetylation>95%, viscosity
100~200mPas) it is dissolved in 10% acetic acid aqueous solution of 40mL, 160mL methanol dilution is added, presses amino under agitation
0.5 times of addition n-caproic anhydride 5.9mmol of amount of substance is placed 260mL acetone is added afterwards for 24 hours as precipitating at room temperature
Agent, sediment respectively wash three times through methanol and ether, and freeze-drying obtains the positive caproyl chitosan of white water-soluble solid N-
(A6CS).Wherein the calculation method of n-caproic anhydride dosage is described referring to step (1) in embodiment 1.
(2) carboxy methylation of the positive caproyl chitosan of N-：Take 1.128g A6CS is added in 250mL three-necked flask
100mL distilled water, to be completely dissolved at room temperature, taking 10mL concentration is that 10% sodium hydroxide solution is divided into 5 parts, is divided 5 times,
Every minor tick 5min is added in reaction solution, and alkalize 1h.After the completion of alkalization, 4.6g sodium chloroacetate is divided into 5 parts, at interval of
Portion is added into reaction solution in 1min, and 60 DEG C are warming up to after adding, and reacts 2h, the pH of reaction solution is adjusted to neutrality with acetic acid.Instead
It should filter after the completion, filter cake three times, is dialysed three days with acetone washing after washing, is freeze-dried, is obtained the positive caproyl carboxymethyl of N-
Chitosan (A6CMC)。
(3) synthesis of epoxidation poly glycol monomethyl ether：Taking polyethylene glycol monomethyl ether (Mn=1900) 1.9g (1mmol) is molten
In 50mL dry toluene, the tetrahydrofuran of 50mL and the hydrogenation sodium reagent of 0.036g (1.5mmol) are added, is warming up to 25
DEG C, react 4h.0.37mL (4mmol) epoxychloropropane is slowly dropped in reaction solution, 40 DEG C of temperature, reacts 6h.Reaction solution
It is added in the ether of 200mL, filters, relaundered 3 times with ether, be dried in vacuo, product is dissolved into 200mL methylene chloride
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；
(4) synthesis of the positive caproyl carboxymethyl chitosan of N- of poly glycol monomethyl ether grafting：Take 0.317g A6CMC
In the three-necked flask of 250mL, 50mL distilled water is added, the pH=9 of sodium hydrate regulator solution is added, takes 3.916g epoxidation poly-
Glycol monoethyl ether is dissolved in 10mL dry toluene, is added drop-wise in reaction system in 10min by constant pressure funnel, stirring
110 DEG C are warming up to, isothermal reaction is for 24 hours.Reaction solution is dialysed 3 days after the reaction was completed, freeze-drying obtains polyethanol monomethyl ether and connects
The positive bytyry carboxymethyl chitosan of N- of branch is demulsifier 2.
Embodiment 3
The positive bytyry carboxymethyl chitosan of N- of polyethanol monomethyl ether grafting is prepared, specific step is as follows：
(1) synthesis of N- acylation chitosan：2g chitosan (CS) (Mw=179.17kDa, deacetylation>95%, viscosity
100~200mPas) it is dissolved in 10% acetic acid aqueous solution of 40mL, 160mL methanol dilution is added, presses amino under agitation
0.5 times of addition caprylic acid acid anhydride 5.9mmol of amount of substance is placed 260mL acetone is added afterwards for 24 hours as precipitating at room temperature
Agent, sediment respectively wash three times through methanol and ether, and freeze-drying obtains the positive n-octanoylation chitosan of white water-soluble solid N-
(A8CS).Wherein the calculation method of caprylic acid acid anhydride dosage is described referring to step (1) in embodiment 1.
(2) carboxy methylation of the positive n-octanoylation chitosan of N-：Take 1.256g A8CS is added in 250mL three-necked flask
100mL distilled water takes sodium hydroxide solution point 5 times that 10mL concentration is 10%, every minor tick to be completely dissolved at room temperature
5min is added in reaction solution, and alkalize 1h.After the completion of alkalization, 4.6g sodium chloroacetate is divided into 5 parts, is added at interval of 1min a
Into reaction solution, it is warming up to 60 DEG C after adding, reacts 2h.Filter after the reaction was completed, filter cake with acetone washing three times, after washing thoroughly
Analysis three days, freeze-drying, obtains the positive n-octanoylation carboxymethyl chitosan (A of N-8CMC)。
(3) synthesis of epoxidation poly glycol monomethyl ether：Taking polyethylene glycol monomethyl ether (Mn=750) 0.75g (1mmol) is molten
In 50mL dry toluene, the tetrahydrofuran of 50mL and the hydrogenation sodium reagent of 0.036g (1.5mmol) are added, is warming up to 25
DEG C, react 4h.0.37mL (4mmol) epoxychloropropane is slowly dropped in reaction solution, 40 DEG C of temperature, reacts 6h.Reaction solution
It is added in the ether of 200mL, filters, relaundered 3 times with ether, be dried in vacuo, product is dissolved into 200mL methylene chloride
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 ring
Aoxidize poly glycol monomethyl ether；
(4) synthesis of the positive n-octanoylation carboxymethyl chitosan of N- of poly glycol monomethyl ether grafting：Take 0.345g A8CMC
In the three-necked flask of 250mL, 50mL distilled water is added, the pH=9 of sodium hydrate regulator solution is added, takes 1.616g epoxidation poly-
Glycol monoethyl ether is dissolved in 10mL dry toluene, is added drop-wise in reaction system in 10min by constant pressure funnel, stirring
110 DEG C are warming up to, isothermal reaction is for 24 hours.Reaction solution is dialysed 3 days after the reaction was completed, freeze-drying obtains polyethanol monomethyl ether and connects
The positive bytyry carboxymethyl chitosan of N- of branch is demulsifier 3.
Embodiment 4
The positive n-octanoylation carboxylic propyl chitosan of N- of poly- diethanol monomethyl ether grafting is prepared, specific step is as follows：
(1) with step (1) in embodiment 3, the positive n-octanoylation chitosan (A of N- is obtained8CS)。
(2) the carboxylic propylated of the positive n-octanoylation chitosan of N-：Take 1.256g A8CS is added in 250mL three-necked flask
100mL aqueous isopropanol, at room temperature sufficiently swelling take sodium hydroxide solution point 5 times that 10mL concentration is 10%, every minor tick
5min is added in reaction solution, and alkalize 1h.After the completion of alkalization, 5.76g chloro-butyric acid sodium is divided into 5 parts, is added one at interval of 1min
Part is warming up to 70 DEG C into reaction solution after adding, react 7h.Filter after the reaction was completed, filter cake with acetone washing three times, after washing
Dialysis three days, freeze-drying, obtains the positive n-octanoylation carboxylic propyl chitosan (A of N-8CPC)。
(3) synthesis of epoxidation poly glycol monomethyl ether：Taking polyethylene glycol monomethyl ether (Mn=350) 0.35g
(1mmol) is dissolved in 50mL dry toluene, adds the hydrogenation of the tetrahydrofuran and 0.036g (1.5mmol) of 50mL
Sodium reagent is warming up to 25 DEG C, reacts 4h.0.37mL (4mmol) epoxychloropropane is slowly dropped in reaction solution, temperature 40
DEG C, react 6h.Reaction solution is added in the ether of 200mL, filters, is relaundered 3 times with ether, is dried in vacuo, product is dissolved
Into 200mL methylene chloride, it is washed with distilled water liquid separation three times, dry with anhydrous magnesium sulfate, filtrate decompression is distilled after suction filtration,
Freeze-drying obtains epoxidation poly glycol monomethyl ether；
(4) synthesis of the positive n-octanoylation carboxylic propyl chitosan of N- of poly glycol monomethyl ether grafting：Take 0.373g A8CPC
In the three-necked flask of 250mL, 50mL distilled water is added, the pH=10 of sodium hydrate regulator solution is added, takes 0.816g epoxidation
Poly glycol monomethyl ether is dissolved in 10mL dry toluene, is added drop-wise in reaction system, is stirred in 10min by constant pressure funnel
It mixes and is warming up to 110 DEG C, isothermal reaction is for 24 hours.Reaction solution is dialysed 3 days after the reaction was completed, freeze-drying obtains polyethanol monomethyl ether
The positive bytyry carboxylic propyl chitosan of the N- of grafting is demulsifier 4.
Comparative example 1
It is SP series demulsifier as demulsifier comparative example 1 using commercially available trade names.
Comparative example 2
It is JL series demulsifier as demulsifier comparative example 2 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 40~80 DEG C, demulsifier concentration is 70~220ppm 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)》, right respectively
The demulsification performance of demulsifier comparative example 1-2 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 is 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 (20min, 40min, 60min, 80min, 100min, 120min), when terminating sedimentation, observational record sewage face
Color.
Experimental result is shown, compared to demulsifier comparative example 1-3, the demulsifier 1-3 obtained according to the method for the present invention is de-
Coolant-temperature gage is 40~80 DEG C, and demulsifier concentration is to have better dewatering and desalting effect, especially dense within the scope of 70~220ppm
Effect is best when degree is 200ppm, dehydration temperaturre is 50 DEG C.
The demulsifier comparative example 1-2 provided in the demulsifier 1-4 and comparative example 1-2 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.
Table 1
Claims (11)
1. a kind of novel crude oil demulsifier, which is characterized in that have general structure shown in following formula (I)s：
2. a kind of preparation method of novel crude oil demulsifier, which is characterized in that include the following steps：
1) acylation modification is carried out to the amino on chitosan：
Chitosan is dissolved in aqueous solutions of organic acids, Organic Alcohol dilution is added, by the amount of the substance of amino on the chitosan
0.5 times of addition acid anhydrides places 24~48h, and precipitating reagent is added, sediment is washed, and is freeze-dried, obtains N- acylation chitosan；
2) carboxylation alkylation is carried out to N- acylation chitosan to be modified：
N- acylation chitosan made from step 1) is dissolved in or is swollen in solvent A, lye alkalization is added；It, will after the completion of alkalization
Chloro alkyl acid sodium is added in reaction solution, is warming up to 50~100 DEG C, reacts 2~7h；Reaction solution is isolated and purified, and freezing is dry
It is dry, obtain the acylated carboxyalkyl chitosan of N-；Wherein, the carbon chain lengths of the chloro alkyl acid sodium are C2-C18；
3) epoxidation modification is carried out to the terminal hydroxy group of poly glycol monomethyl ether and obtains epoxidation poly glycol monomethyl ether；
4) epoxidation poly glycol monomethyl ether and the acylated carboxyalkyl chitosan reaction of N-, specific step is as follows：
The acylated carboxyalkyl chitosan of the N- being prepared in step 2) is dissolved in or is swollen in solvent D, the pH value of solution is adjusted,
It is added drop-wise in reaction system after the epoxidation poly glycol monomethyl ether that step 3) is prepared is dissolved in solvent B, it is warming up to 80~
120 DEG C, reaction 12~for 24 hours, reaction solution is isolated and purified, freeze-drying, and the N- that must be modified poly- diethanol monomethyl ether grafting is acylated
Carboxyalkyl chitosan.
3. the preparation method of novel crude oil demulsifier according to claim 2, which is characterized in that organic described in step 1)
The volumetric usage of alcohol accounts for 80% of whole system or more.
4. the preparation method of novel crude oil demulsifier according to claim 2, which is characterized in that organic described in step 1)
It is one of fatty alcohol of 1-10 or a variety of that alcohol, which is carbon atom number,；The acid anhydrides is that carbon atom number is right by the fatty acid of 2-10
One of acid anhydrides answered is a variety of；The precipitating reagent is acetone.
5. the preparation method of novel crude oil demulsifier according to claim 2, which is characterized in that in step 2), the N-
The mass parts ratio of acylation chitosan and chloro alkyl acid sodium is (1~1.256):(4.6~15.48).
6. the preparation method of novel crude oil demulsifier according to claim 2, which is characterized in that in step 2), the alkali
The Adding Way of liquid is a small amount of repeatedly addition；The adding manner of the chloro alkyl acid sodium is a small amount of repeatedly addition.
7. the preparation method of novel crude oil demulsifier according to claim 2, which is characterized in that in step 4), the N-
The mass parts ratio of acylated carboxyalkyl chitosan and epoxidation poly glycol monomethyl ether is (0.289~0.821):(0.816~
10.116)。
8. the preparation method of novel crude oil demulsifier according to claim 2, which is characterized in that described molten in step 4)
Liquid pH value range is 9~14.
9. according to the preparation method of the described in any item novel crude oil demulsifiers of claim 2~8, which is characterized in that described molten
Agent A is distilled water, isopropanol, sodium hydroxide solution, hydrochloric acid solution, n,N-Dimethylformamide, n,N-dimethylacetamide, two
First sulfoxide, acetic acid, mixture one or more in methanol；The solvent B is dry toluene；The solvent D is distilled water, different
Propyl alcohol, sodium hydroxide solution, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, acetic acid, one in methanol
Kind is a variety of.
10. the preparation method of novel crude oil demulsifier according to claim 9, which is characterized in that step 3) is specific as follows：
1 molfraction poly glycol monomethyl ether is dissolved in solvent B at room temperature, adds appropriate solvent C and 1~5 molar part alkali
Change reagent, be warming up to 20~40 DEG C, reacts 3~8h, then 2.5~10 molfraction epoxidation reagents are slowly dropped to reaction solution
In, 20~40 DEG C of 3~20h of reaction are warming up to, reaction solution is isolated and purified, is freeze-dried, and obtains epoxidation poly glycol monomethyl ether；
Wherein, the number average molecular weight of the poly glycol monomethyl ether is between 350~5000.
11. the preparation method of novel crude oil demulsifier according to claim 10, which is characterized in that described in step 3)
Alkalizing agent is sodium hydride or sodium hydroxide；The epoxidation reagent is epoxychloropropane；The solvent C be tetrahydrofuran,
One of ethyl alcohol, dimethyl sulfoxide, methylene chloride, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide are a variety of.
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