CN108865221A - A kind of comb polymer oil-in-water type crude oil demulsifier and preparation method thereof - Google Patents
A kind of comb polymer oil-in-water type crude oil demulsifier and preparation method thereof Download PDFInfo
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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 comb polymer oil-in-water type crude oil demulsifiers and preparation method thereof.The general structure of the demulsifier is shown in formula I, and preparation method is as follows：1) modified alkylated chitosan is alkylated to chitosan；2) so modified that be alkylated carboxyalkyl chitosan to alkylated chitosan progress carboxylation alkylation；3) to poly glycol monomethyl ether terminal hydroxy group carry out acroleic acid esterification it is modified acroleic acid esterification poly glycol monomethyl ether；4) modified poly (ethylene glycol) monomethyl ether and alkylation carboxyalkyl chitosan reaction, obtain the alkylation carboxyalkyl chitosan of poly glycol monomethyl ether grafting.The present invention has many advantages, such as from a wealth of sources, natural, nontoxic, good biocompatibility, degradable using chitosan class natural polymer as raw material.Carboxyalkyl, alkyl and polyether lateral chain are introduced in chitosan molecule chain, and by controlling position and the degree of substitution of each substituent group, a series of high-efficient demulsifiers for being appropriate to oil-in-water (O/W) type emulsion can be obtained.
Description
Technical field
The present invention relates to a kind of comb polymer oil-in-water type crude oil demulsifiers and preparation method thereof, belong to petrochemical industry neck
Domain.
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 purpose of the present invention is propose a kind of comb polymer oil-in-water for above-mentioned problems of the prior art
Type crude oil demulsifier and preparation method thereof, the demulsifier is using chitosan class natural polymer as raw material, in chitosan
Carboxyalkyl, alkyl and polyether lateral chain are introduced on strand, obtained demulsifier can be real for oil-in-water (O/W) type crude oil emulsion
Now efficiently demulsification.The preparation method of the demulsifier have raw material sources are extensive, natural, nontoxic, product good biocompatibility, can
Many advantages, such as degradation.
To achieve the above object, technical solution provided by the invention is as follows：
A kind of comb polymer oil-in-water type crude oil demulsifier, which is characterized in that have structure shown in following formula (I)s logical
Formula：
It is specific as follows the present invention also provides the preparation method of the comb polymer oil-in-water type crude oil demulsifier：
A kind of preparation method of comb polymer oil-in-water type crude oil demulsifier, which is characterized in that include the following steps：
1) active hydrogen on chitosan is alkylated modification and obtains alkylated chitosan, the specific steps are：
Using solvent A as reaction medium, chitosan and lye is added, stir and is steadily warming up to 40 DEG C~60 DEG C, constant temperature is anti-
0.5~2h is answered, chitosan is made to alkalize；After alkalization, under same reaction temperature, a certain amount of alkyl halide is slowly added dropwise, it is permanent
4~10h of temperature reaction；Product is washed out, adjusts its pH value as neutrality；Then precipitating reagent is added, product is precipitated sufficiently, sufficient standing
It filters, Washing of Filter Cake, dries after precipitating, dialyse, freeze-drying obtains alkylated chitosan.
2) so modified that be alkylated carboxyalkyl chitosan to alkylated chitosan progress carboxylation alkylation, the specific steps are：
Isopropanol is added into alkylated chitosan made from step 1), is swollen at room temperature, 1~4h of lye alkalization is added；
After the completion of alkalization, carboxylated reagent chloro alkyl acid sodium is added in reaction solution, is warming up to 50~70 DEG C, reacts 3~7h, is adjusted
The pH for saving reaction solution is neutrality；Reaction product is filtered, Washing of Filter Cake dialysis, it is poly- to obtain alkylation carboxyalkyl shell for freeze-drying
Sugar；Wherein it is preferred to which the carbon chain lengths of the chloro alkyl acid sodium are C2-C18。
3) to the terminal hydroxy group of poly glycol monomethyl ether carry out acroleic acid esterification it is modified acroleic acid esterification polyethyleneglycol first
Ether, specific step is as follows：
1 molfraction poly glycol monomethyl ether is dissolved in solvent C at room temperature, is stirred, the catalysis of 1~5 molfraction is added
Agent, then be slowly dropped in reaction solution after 2.5~5 molfraction acrylating reagents are dissolved in solvent C, 20~30h is reacted,
Filtering, vacuum distillation remove solvent, solvent D recrystallization are added three times, vacuum drying obtains acroleic acid esterification polyethyleneglycol first
Ether；Wherein, the number average molecular weight of the poly glycol monomethyl ether is between 350~5000.
4) acroleic acid esterification poly glycol monomethyl ether and alkylation carboxyalkyl chitosan reaction：
The alkylation carboxyalkyl chitosan being prepared in step 2) is dissolved in or is swollen in solvent B, lye tune is added
The pH value for saving solution in a certain range, is dripped after acroleic acid esterification poly glycol monomethyl ether made from step 3) is dissolved in solvent B
It being added in reaction system, stirring heating, temperature is 80~120 DEG C, isothermal reaction 2~for 24 hours, reaction solution is dialysed, is freeze-dried,
Obtain the alkylation carboxyalkyl chitosan of poly glycol monomethyl ether grafting.
According to the above scheme, it is preferable that in step 1), the amount ratio of the chitosan and the alkyl halide is 1g:(1.5~
3)mL。
According to the above scheme, it is preferable that solvent A described in step 1) is one of distilled water or Organic Alcohol or two kinds
Mixture, wherein it is in the fatty alcohol of 1-10 that the Organic Alcohol, which is the carbon atom numbers such as methanol, ethyl alcohol, normal propyl alcohol, isobutanol,
It is one or more；The lye is one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or a variety of；The alkyl halide
Alkyl halide corresponding to the alkane for being 4-16 for carbon atom number；The precipitating reagent is acetone.
According to the above scheme, it is preferable that in step 2), the mass parts ratio of the alkylated chitosan and chloro alkyl acid sodium
For (0.93~1.35):(2.9~8.5).
According to the above scheme, it is preferable that in step 2), the adding manner of the lye is a small amount of repeatedly addition；It is alkalizing
Cheng Hou, the adding manner of the carboxylated reagent chloro alkyl acid sodium are a small amount of repeatedly addition.
According to the above scheme, it is preferable that in step 3), the catalyst is pyridine or triethylamine；The acroleic acid esterification examination
Agent is acryloyl chloride.
By stating scheme, it is preferable that in step 4), the alkylation carboxyalkyl chitosan and acroleic acid esterification polyethyleneglycol
The mass parts ratio of methyl ether is (0.377~0.573):(0.844~10.144)；
By stating scheme, it is preferable that in step 4), the solution ph range is 7~10.
In above scheme, it is preferable that the solvent B 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 C is one of tetrahydrofuran, methylene chloride, acetonitrile, ether or more
Kind.
According to the above scheme, it is preferable that the solvent D is one of ether, isopropyl ether, methyl tertiary butyl ether(MTBE) or a variety of.
Synthetic route of the invention is as follows：
1, monomethyl polyethylene glycol acrylate esterization is modified：
2, preparation alkylation carboxyalkyl chitosan, the alkylation carboxyalkyl chitosan of synthesizing polyethylene glycol monomethyl ether grafting：
Aiming at the problems existing in the 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 carboxyalkylalkyl chitosan 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
It, can be real for oil-in-water (O/W) type crude oil emulsion with the naturally occurring emulsifying agents such as pitch, paraffin, resin of displacement adsorbed on interfaces
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 polyethers of chain length, perhaps change reaction raw materials amount ratio or change reaction system reaction temperature and when
Between etc. conditions, to change demulsifier molecular structure such as molecular weight, degree of substitution, hydrophobic segment length aggregated structure etc., in turn
Regulate and control the de-oiling effect of the high-efficient demulsifier of synthesis, to be suitable for the original of heterogeneity (different sources, oil-containing water content are different)
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.
Unless otherwise instructed, all raw materials referred in following embodiments are commercially available acquisition.
Embodiment 1
The preparation of the butyl carboxymethyl chitosan of poly glycol monomethyl ether grafting, specific step is as follows：
(1) preparation of butyl chitosan：Precise 1.0g chitosan (CS) (Mw=179.17kDa, deacetylation>
95%, 100~200mPas of viscosity) in 250mL three-necked flask, 12mL isopropanol, 2g potassium hydroxide, stirring condition is added
It is steadily warming up to 40 DEG C and constant temperature 2h down so that chitosan alkalizes.After alkalization, 3mL is slowly added dropwise under same reaction temperature
Bromination of n-butane, isothermal reaction 6h.20mL methanol is added to wash out product into three-necked flask after the reaction was completed.It is with mass fraction
10mL acetone is added as precipitating reagent in 10% dilute hydrochloric acid regulation system pH=7, and sufficient standing filters after precipitating, filter cake first
Pure and mild ether respectively washs three times, 80 DEG C of oven overnights, dialyses, and freeze-drying obtains faint yellow solid butyl chitosan (BCTS).
(2) preparation of butyl carboxymethyl chitosan：It takes 0.93g BCTS in 250mL three-necked flask, 50mL isopropyl is added
Alcohol, room temperature are swollen 30min, take sodium hydroxide solution point 5 times that 10mL concentration is 10%, every minor tick 5min is added to reaction solution
In, alkalize 2h.After the completion of alkalization, 2.9g sodium chloroacetate is divided into 5 parts, portion is added into reaction solution at interval of 1min, adds
After be warming up to 60 DEG C, react 4h, the pH of reaction solution be adjusted to neutrality with acetic acid.It filters after the reaction was completed, filter cake is washed with acetone
It washs three times, dialyses three days after washing, be freeze-dried, obtain butyl carboxymethyl chitosan (BCMC).
(3) synthesis of acroleic acid esterification poly glycol monomethyl ether：Taking polyethylene glycol monomethyl ether (Mn=5000) 5g (1mmol)
It is dissolved in 30mL acetonitrile solution, stirs at room temperature, the triethylamine of 0.4mL (3mmol) is added, by 0.36g (4mmol) acryloyl chloride
It is dissolved in 10mL acetonitrile solution and being slowly dropped in reaction solution, react 20h.Filtering, vacuum distillation, is added the ether weight of 200mL
Three times, vacuum drying obtains acroleic acid esterification poly glycol monomethyl ether for crystallization.
(4) synthesis of the butyl carboxymethyl chitosan of poly glycol monomethyl ether grafting：It takes 0.377g BCMC to be added to be equipped with
In the three-necked flask of 50mL dimethyl sulfoxide, the pH=9 of sodium carbonate regulating solution is added, takes the poly- second two of 10.144g acroleic acid esterification
In the molten 10mL dimethyl sulfoxide solution of alcohol monomethyl ether, it is added drop-wise in reaction system, is warming up in 10min with constant pressure funnel
120 DEG C, isothermal reaction is for 24 hours.Reaction solution is dialysed 3 days after the reaction was completed, freeze-drying obtains poly glycol monomethyl ether grafting
Butyl carboxymethyl chitosan is demulsifier 1.
Embodiment 2
The preparation of the hexyl carboxymethyl chitosan of poly glycol monomethyl ether grafting, specific step is as follows：
(1) preparation of hexyl chitosan：Precise 1.0g chitosan (CS) (Mw=179.17kDa, deacetylation>
95%, 100~200mPas of viscosity) in 250mL three-necked flask, 12mL distilled water, 2g potassium hydroxide, stirring condition is added
It is steadily warming up to 40 DEG C and constant temperature 2h down so that chitosan alkalizes.After alkalization, 3mL is slowly added dropwise under same reaction temperature
Bromo n-hexane, isothermal reaction 6h.20mL methanol is added to wash out product into three-necked flask after the reaction was completed.It is with mass fraction
10mL acetone is added as precipitating reagent in 10% dilute hydrochloric acid regulation system pH=7, and sufficient standing filters after precipitating, filter cake first
Pure and mild ether respectively washs three times, 80 DEG C of oven overnights, dialyses, and freeze-drying obtains faint yellow solid hexyl chitosan (HCTS).
(2) preparation of hexyl carboxymethyl chitosan：It takes 1g HCTS in 250mL three-necked flask, 50mL isopropanol is added,
Room temperature is swollen 30min, takes sodium hydroxide solution point 5 times that 10mL concentration is 10%, and every minor tick 5min is added in reaction solution,
Alkalize 2h.After the completion of alkalization, 2.9g sodium chloroacetate is divided into 5 parts, portion is added into reaction solution at interval of 1min, is risen after adding
Temperature reacts 4h, the pH of reaction solution is adjusted to neutrality with acetic acid to 60 DEG C.It filters after the reaction was completed, filter cake acetone washing three
It is secondary, it dialyses three days after washing, is freeze-dried, obtains hexyl carboxymethyl chitosan (HCMC).
(3) synthesis of acroleic acid esterification poly glycol monomethyl ether：Taking polyethylene glycol monomethyl ether (Mn=1900) 1.9g
(1mmol) is dissolved in 30mL acetonitrile solution, is stirred at room temperature, the triethylamine of 0.4mL (3mmol) is added, by 0.36g (4mmol)
Acryloyl chloride, which is dissolved in 10mL acetonitrile solution, to be slowly dropped in reaction solution, and 20h is reacted.200mL is added in filtering, vacuum distillation
Diethyl ether recrystallization three times, vacuum drying, obtain acroleic acid esterification poly glycol monomethyl ether.
(4) synthesis of the hexyl carboxymethyl chitosan of poly glycol monomethyl ether grafting：It takes 0.405g HCMC to be added to be equipped with
In the three-necked flask of 50mL dimethyl sulfoxide, the pH=9 of sodium carbonate regulating solution is added, takes 3.944g acrylate polyethylene glycol
Monomethyl ether is dissolved in 10mL dimethyl sulfoxide solution, is added drop-wise in reaction system, is warming up in 10min with constant pressure funnel
120 DEG C, isothermal reaction is for 24 hours.Reaction solution is dialysed 3 days after the reaction was completed, freeze-drying obtains poly glycol monomethyl ether grafting
Hexyl carboxymethyl chitosan is demulsifier 2.
Embodiment 3
The preparation of the octyl carboxymethyl chitosan of poly glycol monomethyl ether grafting, specific step is as follows：
(1) preparation of octyl chitosan：Precise 1.0g chitosan (CS) (Mw=179.17kDa, deacetylation>
95%, 100~200mPas of viscosity) in 250mL three-necked flask, 6mL distilled water and 12mL isopropanol, 2g hydroxide is added
Potassium is steadily warming up to 40 DEG C and constant temperature 2h under stirring condition so that chitosan alkalizes.After alkalization, under same reaction temperature
3mL n-octane bromide, isothermal reaction 6h is slowly added dropwise.20mL methanol is added to wash out product into three-necked flask after the reaction was completed.With
The dilute hydrochloric acid regulation system pH=7 that mass fraction is 10%, addition 10mL acetone is as precipitating reagent, mistake after sufficient standing precipitates
Filter, filter cake methanol and ether respectively wash three times, 80 DEG C of oven overnights, dialyse, and it is poly- to obtain faint yellow solid octyl shell for freeze-drying
Sugared (OCTS).
(2) preparation of octyl carboxymethyl chitosan：It takes 1.07g OCTS in 250mL three-necked flask, 50mL isopropyl is added
Alcohol, room temperature are swollen 30min, take the certain density sodium hydroxide solution of 10mL point 5 times, and every minor tick 5min is added to reaction solution
In, alkalize 2h.After the completion of alkalization, 2.9g sodium chloroacetate is divided into 5 parts, portion is added into reaction solution at interval of 1min, adds
After be warming up to 60 DEG C, react 4h.It filters after the reaction was completed, filter cake three times, is dialysed three days with acetone washing after washing, and freezing is dry
It is dry, obtain octyl carboxymethyl chitosan (OCMC).
(3) synthesis of acroleic acid esterification poly glycol monomethyl ether：Taking polyethylene glycol monomethyl ether (Mn=750) 0.75g
(1mmol) is dissolved in 30mL acetonitrile solution, is stirred at room temperature, the triethylamine of 0.4mL (3mmol) is added, by 0.36g (4mmol)
Acryloyl chloride, which is dissolved in 10mL acetonitrile solution, to be slowly dropped in reaction solution, and 20h is reacted.200mL is added in filtering, vacuum distillation
Diethyl ether recrystallization three times, vacuum drying obtain acroleic acid esterification poly glycol monomethyl ether；
(4) synthesis of the octyl carboxymethyl chitosan of poly glycol monomethyl ether grafting：It takes 0.433g OCMC to be added to be equipped with
In the three-necked flask of 50mL dimethyl sulfoxide, the pH=9 of sodium carbonate regulating solution is added, takes 1.644g acrylate polyethylene glycol
Monomethyl ether is dissolved in 10mL dimethyl sulfoxide solution, is added drop-wise in reaction system, is warming up in 10min with constant pressure funnel
120 DEG C, isothermal reaction is for 24 hours.Reaction solution is dialysed 3 days after the reaction was completed, freeze-drying obtains poly glycol monomethyl ether grafting
Octyl carboxymethyl chitosan is demulsifier 3.
Embodiment 4
The preparation of the octyl carboxylic propyl chitosan of poly glycol monomethyl ether grafting, specific step is as follows：
(1) with step (1) in embodiment 3, octyl chitosan (OCTS) is obtained.
(2) preparation of octyl carboxylic propyl chitosan：It takes 1.07g OCTS in 250mL three-necked flask, 50mL isopropyl is added
Alcohol, room temperature are swollen 30min, take the certain density sodium hydroxide solution of 10mL point 5 times, and every minor tick 5min is added to reaction solution
In, alkalize 2h.After the completion of alkalization, 3.7g chloro-butyric acid sodium is divided into 5 parts, portion is added into reaction solution at interval of 1min, adds
After be warming up to 60 DEG C, react 4h.It filters after the reaction was completed, filter cake three times, is dialysed three days with acetone washing after washing, and freezing is dry
It is dry, obtain octyl carboxylic propyl chitosan (OCPC).
(3) synthesis of acroleic acid esterification poly glycol monomethyl ether：Taking polyethylene glycol monomethyl ether (Mn=350) 0.35g
(1mmol) is dissolved in 30mL acetonitrile solution, is stirred at room temperature, the triethylamine of 0.4mL (3mmol) is added, by 0.36g (4mmol)
Acryloyl chloride, which is dissolved in 10mL acetonitrile solution, to be slowly dropped in reaction solution, and 20h is reacted.200mL is added in filtering, vacuum distillation
Diethyl ether recrystallization three times, vacuum drying obtain acroleic acid esterification poly glycol monomethyl ether；
(4) synthesis of the octyl carboxylic propyl chitosan of poly glycol monomethyl ether grafting：It takes 0.461gOCPC to be added to be equipped with
50mLN in the three-necked flask of dinethylformamide, is added the pH=9 of sodium carbonate regulating solution, takes 0.844g acroleic acid esterification
Poly glycol monomethyl ether is dissolved in 10mLN, in dinethylformamide solution, is added drop-wise in 10min with constant pressure funnel anti-
It answers in system, is warming up to 120 DEG C, isothermal reaction is for 24 hours.Reaction solution is dialysed 3 days after the reaction was completed, freeze-drying obtains poly- second
The octyl carboxylic propyl chitosan of glycol monomethyl ether 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 1-2, the demulsifier 1-4 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 (10)
1. a kind of comb polymer oil-in-water type crude oil demulsifier, which is characterized in that have structure shown in following formula (I)s logical
Formula：
2. a kind of preparation method of comb polymer oil-in-water type crude oil demulsifier, which is characterized in that include the following steps：
1) modification is alkylated to the active hydrogen on chitosan：
Using solvent A as reaction medium, chitosan and lye is added, is warming up to 40 DEG C~60 DEG C, 0.5~2h is reacted, then in phase
With under reaction temperature, alkyl halide is added dropwise, reacts 4~10h；Product is washed out, adjusts its pH value as neutrality；Then precipitating reagent is added,
It is filtered after precipitating, after filter cake is purified, freeze-drying obtains alkylated chitosan；
2) carboxylation alkylation is carried out to alkylated chitosan to be modified：
Isopropanol is added into alkylated chitosan made from step 1), is swollen at room temperature, 1~4h of lye alkalization is added；Alkalization
After the completion, chloro alkyl acid sodium is added in reaction solution, is warming up to 50~70 DEG C, react 3~7h；Reaction product is pure through separating
Change, freeze-drying, obtains alkylation carboxyalkyl chitosan；Wherein, the carbon chain lengths of the chloro alkyl acid sodium are C2-C18；
3) to the terminal hydroxy group of poly glycol monomethyl ether carry out acroleic acid esterification it is modified acroleic acid esterification poly glycol monomethyl ether；
4) acroleic acid esterification poly glycol monomethyl ether and alkylation carboxyalkyl chitosan reaction：
The alkylation carboxyalkyl chitosan being prepared in step 2) is dissolved in or is swollen in solvent B, it is molten that lye adjusting is added
The pH value of liquid is added drop-wise in reaction system after acroleic acid esterification poly glycol monomethyl ether made from step 3) is dissolved in solvent B, is risen
Temperature to 80~120 DEG C, reaction 2~for 24 hours, reaction solution is dialysed, is freeze-dried, obtain poly glycol monomethyl ether grafting alkylation carboxylic
Alkyl chitosan.
3. the preparation method of comb polymer oil-in-water type crude oil demulsifier according to claim 2, which is characterized in that step
It is rapid 1) described in the amount ratio of chitosan and the alkyl halide be 1g:(1.5~3) mL.
4. the preparation method of comb polymer oil-in-water type crude oil demulsifier according to claim 2, which is characterized in that step
It is rapid 1) described in solvent A be one of distilled water or Organic Alcohol or two kinds of mixture, wherein the Organic Alcohol be carbon
Atomicity is one of fatty alcohol of 1-10 or a variety of；The alkyl halide is halogen corresponding to alkane that carbon atom number is 4-16
For alkane；The precipitating reagent is acetone.
5. the preparation method of comb polymer oil-in-water type crude oil demulsifier according to claim 2, which is characterized in that step
It is rapid 2) in, the mass parts ratio of the alkylated chitosan and chloro alkyl acid sodium is (0.93~1.35):(2.9~8.5).
6. the preparation method of comb polymer oil-in-water type crude oil demulsifier according to claim 2, which is characterized in that institute
The adding manner for stating lye is a small amount of repeatedly addition；The adding manner of the carboxylated reagent chloro alkyl acid sodium is a small amount of multiple
It is added.
7. the preparation method of comb polymer oil-in-water type crude oil demulsifier according to claim 2, which is characterized in that step
It is rapid 4) in, it is described alkylation carboxyalkyl chitosan and acroleic acid esterification poly glycol monomethyl ether mass parts ratio be (0.377~
0.573):(0.844~10.144).
8. the preparation method of comb polymer oil-in-water type crude oil demulsifier according to claim 2, which is characterized in that step
It is rapid 4) in, the solution ph range be 7~10；The solvent B is that distilled water, isopropanol, sodium hydroxide solution, hydrochloric acid are molten
Liquid, n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl sulfoxide, acetic acid, mixture one or more in methanol.
9. special according to the preparation method of the described in any item comb polymer oil-in-water type crude oil demulsifiers of claim 2~8
Sign is that step 3) is specific as follows：
1 molfraction poly glycol monomethyl ether is dissolved in solvent C at room temperature, is stirred, 1~5 molfraction catalyst is added, then
It is slowly dropped in reaction solution after 2.5~5 molfraction acrylating reagents are dissolved in solvent A, reacts 20~30h, filtered,
Vacuum distillation removes solvent, and solvent D recrystallization is added three times, and vacuum drying obtains acroleic acid esterification poly glycol monomethyl ether；Its
In, the number average molecular weight of the poly glycol monomethyl ether is between 350~5000.
10. the preparation method of comb polymer oil-in-water type crude oil demulsifier according to claim 9, which is characterized in that
In step 3), the solvent C is one of tetrahydrofuran, methylene chloride, acetonitrile, ether or a variety of；The solvent D is second
One of ether, isopropyl ether, methyl tertiary butyl ether(MTBE) are a variety of；The catalyst is pyridine or triethylamine；The acroleic acid esterification
Reagent is acryloyl chloride.
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| WO2004050801A1 (en) * | 2002-12-03 | 2004-06-17 | M-I L.L.C. | Demulsifiers for crude oil emulsions |
| CN103320158A (en) * | 2013-07-10 | 2013-09-25 | 武汉工程大学 | Natural polysaccharide macromolecule-modified crude oil demulsifier |
| CN106117562A (en) * | 2016-08-09 | 2016-11-16 | 武汉工程大学 | A kind of preparation method of comb polymer crude oil desalting demulsifier |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004050801A1 (en) * | 2002-12-03 | 2004-06-17 | M-I L.L.C. | Demulsifiers for crude oil emulsions |
| CN103320158A (en) * | 2013-07-10 | 2013-09-25 | 武汉工程大学 | Natural polysaccharide macromolecule-modified crude oil demulsifier |
| CN106117562A (en) * | 2016-08-09 | 2016-11-16 | 武汉工程大学 | A kind of preparation method of comb polymer crude oil desalting demulsifier |
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