CN107162154A - A kind of ternary composite flooding water extraction support type reverse-phase emulsifier and preparation method thereof - Google Patents
A kind of ternary composite flooding water extraction support type reverse-phase emulsifier and preparation method thereof Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
A kind of ternary composite flooding water extraction support type reverse-phase emulsifier and preparation method thereof, belongs to oil-polluted water demulsifier and preparation method thereof.Reverse-phase emulsifier basic framework is synthesized by hydrosilylation first, polyquaternium and co-modified silicone oil are then subjected to epoxy additionization reaction synthesizing polyether polyquaternium reverse-phase emulsifier, then using silane coupler KH 570 to hydrated SiO 2 (SiO2·nH2O) surface carries out hydrophobically modified, and polyethers polyquaternium reverse-phase emulsifier and modified hydrated SiO 2 finally are carried out into surface scion grafting polymerisation, support type reverse-phase emulsifier is prepared.Support type reverse-phase emulsifier is demulsified by being supported on polyethers polyquaternium reverse-phase emulsifier replacement displacement and neutralization interfacial film charge effect on modified hydration silica supports particle, oil droplet demulsification is adsorbed and sedimentation separation rapidly after taking off surely by carrier particle, so as to complete demulsification, adsorption process.The support type reverse-phase emulsifier of offer has that de-oiling rate is high, consumption is few, water-oil separating speed is fast, it is easily separated the features such as.
Description
Technical field
The present invention relates to a kind of oil-polluted water demulsifier and preparation method thereof, particularly a kind of ternary composite flooding water extraction is born
Load type reverse-phase emulsifier and preparation method thereof.
Background technology
Oil field produced water process is the important leverage of the continual and steady high yield in oil field and ecological environmental protection.Oil exploitation is undergone
Primary oil recovery, secondary oil recovery and tertiary oil recovery three phases, the recovery ratios of three phases is respectively 10%~15%, 30%~
50%th, 50%~70%.At present, each main force oil field of China has been enter into intermediary and later stages High water cut mining phase, is that constant rate of production is needed
The yield of oil, the increase of recovered water sustained production are continued to increase, China about needs to handle more than 10 hundred million m every year3Oil field extracted water.
Therefore, oilfield produced waste water processing is mining site oil field development and the important topic faced of preserving the ecological environment.
Ternary composite flooding water extraction is treated as one of technical bottleneck of ternary composite driving Technique Popularizing.Ternary composite driving is
Refer to injection alkali, a kind of tertiary oil recovery technology of three kinds of chemical agent mixed solutions of surfactant and polymer, carried than common water drive
More than 20 percentage points of high recovery rate, the technology serves important function to the stable yields for being kept for China's oil field later stage.Tri compound
Drive water exit water quality is complicated, high salinity, oil-containing emulsification degree height is presented, interfacial film strength is high, small particle suspension is high, small oil
High particle size content, viscosity height, the low feature of interfacial tension are dripped, phase is stable, and water-oil separating difficulty is big, limits ternary composite driving
The popularization of oil recovery technique.
The de- demulsification of emulsion is surely the key link for improving ternary composite flooding water extraction treatment effeciency.Ternary composite driving is adopted
The surfactant contained in water outlet reduces oil water interfacial tension and Zeta potential, increases the Interfacial elasticity of oil droplet, makes oil
Drop is difficult to de- steady and coalescence.Polymer adds recovered water viscosity, increases negative charge density and Interfacial elasticity.Alkali energy and crude oil
Middle acid substance reacts, and produces some surface reactive materials, increases the negative charge density of oil droplets, enhances the stabilization of oil droplet
Property.The key of ternary composite flooding water extraction processing is to change oil droplets property to make oil droplet demulsification de- steady, and small oil droplet being capable of coalescence
Into larger oil droplet, accelerate water-oil separating speed.
Conventional breaking method is divided into Physical (settling methods, filtration method, centrifugal process, air supporting demulsification, embrane method, microwave
Demulsification, electric field demulsification etc.), chemical method (demulsification medicament), bioanalysis.Chemical demulsification method is a kind of energy strong adsorption of selection in profit
The surfactant at interface, the emulsifying agent of firm film is generated to replace in emulsion, so as to form a kind of new film.New boundary
Facial mask thinner thickness, film strength is significantly reduced and is demulsified.Chemical method demulsification is due to efficiency high, practical, in actual production
In it is most widely used.
At present, mainly there are low molecule electrolyte, alcohol for the reverse-phase emulsifier that O/W type emulsion breakdowns are used both at home and abroad
Class, surfactant-based and high molecular polymer three major types.Electrolyte, alcohols demulsification are limited, dosage big, and easily shape
Into secondary pollution, eliminate and used.Surfactant-based demulsifier mainly has cationic, anionic and non-ionic.Sun
Ionic surface active agent is mainly quaternary ammonium salt, and anion surfactant is mainly dithiocar-bamate, non-ionic
Surfactant is mainly polyamine class.High molecular polymerization species reverse-phase emulsifier includes polyether-type, polyquaternium, polysiloxanes etc.
Type.Polyquarternium-type demulsifier possesses good water solubility, the advantages of diffusion velocity is fast.Polysiloxanes have high chemical stability,
Low surface tension and strong hydrophobicity, in the good advantage of the interface diffusivity of O/W type emulsions.The research of demulsifier had in recent years
Considerable progress, such as US5045212 disclose the rp demulsification of a kind of organic cation demulsifier and inorganic salts demulsifier compound
Agent, EP0331323A2 discloses a kind of amine high-molecular compound demulsifier for being suitable for oil extraction, CN201310534158
A kind of magnetic antiphase demulsifier for the oily waste water treatment being suitable for during oil exploitation is disclosed, CN200810115284 makes
A kind of stellate poly quaternary ammonium salt reverse-phase emulsifier is mixed to get with polyamide-amide quaternary ammonium salt and linear quaternary ammonium salt (LPQA),
Reverse-phase emulsifier made from CN201210035036 is by cationic polyamide-amine, Hydrin quaternary ammonium salt and polypropylene
Acyloxyethyl trimethyl ammonium chloride is constituted.But oil droplet size is fine in ternary composite flooding water extraction, oil-containing emulsification degree is high, interface
Film-strength is high, and demulsification difficulty is big.Ternary composite flooding water extraction demulsification system is that a demulsifier coexists with emulsifying agent, and be demulsified process
Coexisted with emulsion process, and the reversible complex system of demulsification process, therefore, it is adapted to the new height of ternary composite flooding water extraction demulsification
The demulsifier of effect needs further exploitation.
The content of the invention
Technical problem：The invention aims to provide a kind of ternary composite flooding water extraction support type reverse-phase emulsifier and its
Preparation method, the problem of solving ternary composite flooding water extraction hardly possible demulsification.
Technical scheme：The object of the present invention is achieved like this：Ternary composite flooding water extraction demulsifier of the present invention includes：It is negative
Load type reverse-phase emulsifier and support type reverse-phase emulsifier preparation method.
Support type reverse-phase emulsifier, its structural formula is as follows：
Wherein, x1=1~30；x2=1~30；x3=1~20；Y=1~50；A=7~19；B=1~19；M=9~
10；N=1~3.
The preparation method of support type reverse-phase emulsifier：The basic bone of reverse-phase emulsifier is synthesized by hydrosilylation first
Frame, then carries out epoxy additionization reaction synthesizing polyether polyquaternium reverse-phase emulsifier by polyquaternium and co-modified silicone oil, then
Using Silane coupling reagent KH-570 to hydrated SiO 2 (SiO2·nH2O) surface carries out hydrophobically modified, finally by polyethers poly- season
Ammonium salt reverse-phase emulsifier and modified hydrated SiO 2 carry out surface scion grafting polymerisation, prepare support type reverse-phase emulsifier.
Comprise the following steps that：
1) the basic framework synthesis of rp demulsification agent molecule
After ether epoxy, methyl ether are mixed with containing hydrogen silicone oil, catalyst chloroplatinic acid is added, stirring 20min~30min is put
In microwave reactor, 10min~40min is reacted under microwave power 100W~500W, reaction product is fully molten with n-hexane
Solution, is isolated after undissolved product, and revolving removes a small amount of solvent, then is dried in vacuo 24h at 60 DEG C, obtains ether epoxy methyl ether
Co-modified silicone oil intermediate；
2) polyquaternium is synthesized
Dibutyl amine and organic amine crosslinking agent are sequentially added in the reactor with condensing unit, nitrogen is passed through and stirs
Mix, epoxychloropropane is slowly added at 10 DEG C~30 DEG C, heated up 1h to 40 DEG C~80 DEG C after the completion of adding, continue stirring reaction
3~8h, cooling obtains yellow viscous liquid product, and reaction product is used into 1:1 absolute ethyl alcohol-acetone is rotated after fully washing and removed
Solvent, then 24h is dried in vacuo at 70 DEG C, obtain product polyquaternium；
3) polyethers polyquarternium-type reverse-phase emulsifier is synthesized
Polyquaternium and alcohols solvent are sequentially added into the reactor with condensing unit, nitrogen is passed through and stirs,
Add co-modified silicone oil at 25 DEG C~45 DEG C, 3~7h of stirring reaction, after cooling, product uses 1:1 absolute ethyl alcohol-acetone soln is more
Secondary washing, revolving removes solvent, is dried in vacuo 24h, as products therefrom polyethers polyquaternium PPA；
4) hydrophobically modified of carrier hydrated SiO 2
It is added to after hydrated SiO 2 and silane coupler are sufficiently mixed in alcohols solvent, stirs 20min~30min
Catalyst methane sulfonic acid is added afterwards, 16h~32h is stirred at reflux at 35 DEG C~60 DEG C, after reaction terminates, with ethanol wash products 3
~5 times, 12h~14h is dried in vacuo at 70 DEG C~90 DEG C, hydrophobically modified hydrated SiO 2 is obtained；
5) synthesis of support type reverse-phase emulsifier
Hydrophobically modified hydrated SiO 2, polyethers polyquaternium PPA and alcohol are added into the reactor with heat-exchanger rig
Class solvent, is passed through nitrogen and stirs, and catalyst chloroplatinic acid is added after 5min, 6h~10h is stirred at reflux at 30 DEG C~50 DEG C, instead
After should terminating, successively repeatedly washed with isopropanol, ethanol, then 24h is dried at 120 DEG C, that is, obtain final products SiO2@PPA。
Preparation process 1) in add ether epoxy be allyl polyethenoxy polyoxypropylene epoxy radicals ether -1, EO:PO=10:
1st, allyl polyethenoxy polyoxypropylene epoxy radicals ether -2, EO:PO=3:1；The methyl ether of addition is poly- for allyl polyethenoxy
Oxypropylene methyl ether -1, EO:PO=1:1st, allyl polyethenoxy polyoxypropylene methyl ether -2, EO:PO=7:1；Described contains
The hydrogeneous mass percent amount of hydrogen silicone oil is 0.1%~0.25%；The ether epoxy and methyl ether mol ratio 1:5~5:1, silicon hydrogen
The mol ratio of key and carbon-carbon double bond is 1:1.0~1:1.2, catalyst chloroplatinic acid consumption is the μ g/g of 10 μ g/g~50.
Preparation process 2) described in epoxychloropropane and dibutyl amine mol ratio be 1:0.9~1:1.4；The organic amine is handed over
Connection agent is ethylenediamine, n-butylamine, polyethylene polyamine, and organic amine dosage is the 1%~15% of reactant quality percentage.
Preparation process 3) described in alcohols solvent be methanol, ethanol or isopropanol；Described polyquaternium, altogether modified silicon
Oil, the mass ratio of alcohols solvent are 0.8~1.2:0.5~2.5:15~30.
Preparation process 4) described in silane coupler be 3- methacryloxypropyl trimethoxy silanes；Described
Alcohols solvent is methanol, ethanol or isopropanol, and the mass ratio of the alcohols solvent, water and Loprazolam is 1:1:0.03~
0.07；Described granular hydrated silica particle size distribution range is 10~100 μm, hydrated SiO 2 and silane coupler matter
Amount is than being 0.8~1.2:2.0~10.0.
Preparation process 5) described in alcohols solvent be methanol, ethanol or isopropanol；Hydrophobically modified silica, polyethers poly- season
Ammonium salt PPA is 0.6~0.8 with alcohols solvent mass ratio:0.8~1.2:2.0~3.0；Catalyst chloroplatinic acid consumption is 40 μ g/g
~80 μ g/g.
Beneficial effect, as a result of such scheme, support type reverse-phase emulsifier of the invention and preparation method thereof is to adopt
Polyethers polyquaternium reverse-phase emulsifier PPA is bonded to specific surface area is big, porous modified be hydrated with surface scion grafting polymerization
Silica (SiO2·nH2O) surface, prepares support type polyethers polyquaternium reverse-phase emulsifier.Support type reverse-phase emulsifier is demulsified
Effect be that displacement demulsification is replaced by polyethers polyquaternium reverse-phase emulsifier and interfacial film electric charge demulsification is neutralized, destruction is former
There is oil-water interface film, replaced by being supported on polyethers polyquaternium reverse-phase emulsifier on modified hydration silica supports particle
Replace and neutralize interfacial film charge effect and be demulsified；Oil droplet after demulsification takes off surely can be supported the carrier of type reverse-phase emulsifier rapidly
Particle is adsorbed, and oil droplet demulsification is adsorbed and sedimentation separation rapidly after taking off surely by carrier particle, completes demulsification, adsorption process.
The support type reverse-phase emulsifier that the present invention is provided has the double effects of demulsification and absorption concurrently.Support type reverse-phase emulsifier
It is broken that the polyethers polyquaternium reverse-phase emulsifier loaded on carrier particle replaces displacement by polyethers polyquaternium reverse-phase emulsifier
Breast and neutralize the demulsification of interfacial film electric charge and be demulsified, with reduction Organic substance in water content the characteristics of, be suitable for oil-polluted water
The particularly demulsification processing of ternary composite flooding water extraction, the oil droplet after demulsification can be adsorbed rapidly by carrier particle, can made after demulsification
Reversible emulsification occurs for micro-size fraction oil droplet, and carrier particle is the characteristics of have easily separated recovery.Solution ternary is solved to answer
The difficult demulsification problem of drive water exit is closed, the purpose of the present invention has been reached.
Advantage：The support type reverse-phase emulsifier of the present invention has that de-oiling rate is high, consumption is few, water-oil separating speed fast, easily point
From making ternary composite flooding water extraction demulsification de- steady, accelerate water-oil separating speed, the processing applied to oil exploitation oil-polluted water
Field.
Brief description of the drawings：
Fig. 1 is the support type reverse-phase emulsifier demulsification of the present invention, absorbing synergic action principle figure.
Fig. 2 is the infrared spectrum comparison diagram of containing hydrogen silicone oil and obtained co-modified silicone oil in the embodiment of the present invention 2.
Fig. 3 is the polyquaternium prepared in the embodiment of the present invention 2 and the infrared spectrum comparison diagram of polyethers polyquaternium.
Fig. 4 is that hydrated SiO 2 in the embodiment of the present invention 2 and obtained hydrophobically modified silica and support type are anti-phase
The infrared spectrum comparison diagram of demulsifier.
Fig. 5 is the xps energy spectrum analysis of support type reverse-phase emulsifier in the embodiment of the present invention 2.
Fig. 6 is ternary composite flooding water extraction treatment effect comparison diagram in the embodiment of the present invention 1.
Fig. 7 is ternary composite flooding water extraction treatment effect comparison diagram in present example 4.
Embodiment
The present invention includes：Support type reverse-phase emulsifier and its support type reverse-phase emulsifier preparation method.
Support type reverse-phase emulsifier, its structural formula is as follows：
Wherein, x1=1~30；x2=1~30；x3=1~20；Y=1~50；A=7~19；B=1~19；M=9~
10；N=1~3.
Support type reverse-phase emulsifier and preparation method thereof：The basic bone of reverse-phase emulsifier is synthesized by hydrosilylation first
Frame, then carries out epoxy additionization reaction synthesizing polyether polyquaternium reverse-phase emulsifier by polyquaternium and co-modified silicone oil, then
Using Silane coupling reagent KH-570 to hydrated SiO 2 (SiO2·nH2O) surface carries out hydrophobically modified, finally by polyethers poly- season
Ammonium salt reverse-phase emulsifier and modified hydrated SiO 2 carry out surface scion grafting polymerisation, prepare support type reverse-phase emulsifier.
Comprise the following steps that：
1) the basic framework synthesis of rp demulsification agent molecule
After ether epoxy, methyl ether are mixed with containing hydrogen silicone oil, catalyst chloroplatinic acid is added, stirring 20min~30min is put
In microwave reactor, 10min~40min is reacted under microwave power 100W~500W, reaction product is fully molten with n-hexane
Solution, is isolated after undissolved product, and revolving removes a small amount of solvent, then is dried in vacuo 24h at 60 DEG C, obtains ether epoxy methyl ether
Co-modified silicone oil intermediate；
2) polyquaternium is synthesized
Dibutyl amine and organic amine crosslinking agent are sequentially added in the reactor with condensing unit, nitrogen is passed through and stirs
Mix, epoxychloropropane is slowly added at 10 DEG C~30 DEG C, heated up 1h to 40 DEG C~80 DEG C after the completion of adding, continue stirring reaction
3~8h, cooling obtains yellow viscous liquid product, and reaction product is used into 1:1 absolute ethyl alcohol-acetone is rotated after fully washing and removed
Solvent, then 24h is dried in vacuo at 70 DEG C, obtain product polyquaternium；
3) polyethers polyquarternium-type reverse-phase emulsifier is synthesized
Polyquaternium and alcohols solvent are sequentially added into the reactor with condensing unit, nitrogen is passed through and stirs,
Add co-modified silicone oil at 25 DEG C~45 DEG C, 3~7h of stirring reaction, after cooling, product uses 1:1 absolute ethyl alcohol-acetone soln is more
Secondary washing, revolving removes solvent, is dried in vacuo 24h, as products therefrom polyethers polyquaternium PPA；
4) hydrophobically modified of carrier hydrated SiO 2
It is added to after hydrated SiO 2 and silane coupler are sufficiently mixed in alcohols solvent, stirs 20min~30min
Catalyst methane sulfonic acid is added afterwards, 16h~32h is stirred at reflux at 35 DEG C~60 DEG C, after reaction terminates, with ethanol wash products 3
~5 times, 12h~14h is dried in vacuo at 70 DEG C~90 DEG C, hydrophobically modified hydrated SiO 2 is obtained；
5) synthesis of support type reverse-phase emulsifier
Hydrophobically modified hydrated SiO 2, polyethers polyquaternium PPA and alcohol are added into the reactor with heat-exchanger rig
Class solvent, is passed through nitrogen and stirs, and catalyst chloroplatinic acid is added after 5min, 6h~10h is stirred at reflux at 30 DEG C~50 DEG C, instead
After should terminating, successively repeatedly washed with isopropanol, ethanol, then 24h is dried at 120 DEG C, that is, obtain final products SiO2@PPA。
Preparation process 1) in add ether epoxy be allyl polyethenoxy polyoxypropylene epoxy radicals ether -1, domestic goods product
The trade mark is DEG-501, EO:PO=10:1st, allyl polyethenoxy polyoxypropylene epoxy radicals ether -2, domestic goods brand number is
DEG-502, EO:PO=3:1；The methyl ether of addition is allyl polyethenoxy polyoxypropylene methyl ether -1, domestic goods brand
Number be DEM-2002, EO:PO=1:1st, allyl polyethenoxy polyoxypropylene methyl ether -2；Domestic goods brand number is DEM-
402EO:PO=7:1；The hydrogeneous mass percent amount of described containing hydrogen silicone oil is 0.1%~0.25%；The ether epoxy and first
Base ether mol ratio 1:5~5:1, the mol ratio of si-h bond and carbon-carbon double bond is 1:1.0~1:1.2, catalyst chloroplatinic acid consumption is
The μ g/g of 10 μ g/g~50.
Preparation process 2) described in epoxychloropropane and dibutyl amine mol ratio be 1:0.9~1:1.4；The organic amine is handed over
Connection agent is ethylenediamine, n-butylamine, polyethylene polyamine, and organic amine dosage is the 1%~15% of reactant quality percentage.
Preparation process 3) described in alcohols solvent be methanol, ethanol or isopropanol；Described polyquaternium, altogether modified silicon
Oil, the mass ratio of alcohols solvent are 0.8~1.2:0.5~2.5:15~30.
Preparation process 4) described in silane coupler be 3- methacryloxypropyl trimethoxy silanes, state's inside trade
Brand number is KH-570；Described alcohols solvent is methanol, ethanol or isopropanol, the alcohols solvent, water and Loprazolam
Mass ratio is 1:1:0.03~0.07；Described granular hydrated silica particle size distribution range is 10~100 μm, is hydrated dioxy
SiClx and silane coupler mass ratio are 0.8~1.2:2.0~10.0.
Preparation process 5) described in alcohols solvent be methanol, ethanol or isopropanol；Hydrophobically modified silica, polyethers poly- season
Ammonium salt PPA is 0.6~0.8 with alcohols solvent mass ratio:0.8~1.2:2.0~3.0；Catalyst chloroplatinic acid consumption is 40 μ g/g
~80 μ g/g.
Support type reverse-phase emulsifier is added in oil-polluted water, by being supported on modified hydration silica supports particle
Polyethers polyquaternium reverse-phase emulsifier replaces displacement demulsification and neutralizes the demulsification of interfacial film electric charge and reach demulsification.Oil droplet is demulsified
It can be adsorbed and sedimentation separation by carrier particle rapidly after taking off surely, so as to complete demulsification, adsorption process.
Technical scheme and technique effect are further described again below by specific embodiment.
Embodiment 1：After the 9.3g of ether epoxy -2, the 4.6g of methyl ether -1 are mixed with containing hydrogen silicone oil 10.0g, 500mg/ is added
L catalyst chloroplatinic acid 2.3mL, stirring 20min is placed in microwave reactor, and 30min, reaction production are reacted under microwave power 300W
Thing n-hexane fully dissolves, and isolates after undissolved product, and revolving removes a small amount of solvent, then is dried in vacuo 24h at 60 DEG C,
Obtain co-modified silicone oil intermediate.Dibutyl amine 19.0g and polyethylene polyamine are sequentially added into the reactor with heat-exchanger rig
Crosslinking agent 1.3g, is passed through nitrogen and stirs, and epoxychloropropane 10.3g is added at 30 DEG C, adds and is heated up 1h to 60 DEG C after end,
Continue stirring reaction 6h, yellow viscous liquid product is obtained after cooling, product is used 1:After 1 absolute ethyl alcohol-acetone is fully washed
Revolving removes solvent, is dried in vacuo 24h at 70 DEG C, obtains polyquaternium；Add successively into the reactor with heat-exchanger rig
Enter polyquaternium 8.33g, isopropanol 15.0g, be passed through nitrogen and stir, co-modified silicone oil 8.3g is added at 35 DEG C, stirring is anti-
5h is answered, with 1 after product cooling:1 absolute ethyl alcohol-acetone soln is washed three times, and revolving is dried in vacuo 24h after removing solvent, produces
To polyethers polyquaternium reverse-phase emulsifier (PPA).In 100mL ternary composite flooding water extractions, wherein alkali content be 700mg/L,
Surface-active contents are 300mg/L, and polymer content is 500mg/L, add 50mg/LPPA and mix, 1h is vibrated at 30 DEG C,
The oil-polluted water oil-water interfaces handled by PPA reverse-phase emulsifiers are clear, and de-oiling rate is 83.4%.
Fig. 1 is ternary composite flooding water extraction treatment effect comparison diagram.Wherein a figures are the ternary that oil concentration is 500mg/L
Composite-driven produced water sample, b figures are the water sample after being handled through PPA demulsifiers.
Embodiment 2：After the 12.4g of ether epoxy -2, the 4.2g of methyl ether -1 are mixed with containing hydrogen silicone oil 15.0g, add
500mg/L catalyst chloroplatinic acid 2.6mL, stirring 20min is placed in microwave reactor, and 20min is reacted under microwave power 200W,
Reaction product n-hexane fully dissolves, and isolates after undissolved product, and revolving removes a small amount of solvent, then vacuum is done at 60 DEG C
Dry 24h, obtains co-modified silicone oil intermediate.Dibutyl amine 19.0g and many second are sequentially added into the reactor with heat-exchanger rig
Alkene polyamine crosslinkers 0.3g, is passed through nitrogen and stirs, and adds epoxychloropropane 10.3g in 30 DEG C of followings, adds the 1h that heated up after end
To 60 DEG C, continue stirring reaction 6h, yellow viscous liquid product is obtained after cooling, product is used 1:1 absolute ethyl alcohol-acetone is abundant
Solvent is removed in revolving after washing, 24h is dried in vacuo at 70 DEG C, obtains polyquaternium；To the reactor with heat-exchanger rig
In sequentially add polyquaternium 8.33g and isopropanol 15.0g, be passed through nitrogen and stir, co-modified silicone oil 10g is added at 35 DEG C,
Product uses 1 after stirring reaction 5h, cooling:1 absolute ethyl alcohol-acetone soln is washed three times, and revolving is removed and is dried in vacuo after solvent
24h, that is, obtain polyethers polyquaternium reverse-phase emulsifier (PPA).By particle size distribution range in 50 μm~100 μm hydrated SiO 2s
Particle 10.0g and silane coupler 20.0g are added in 100g ethanol-water mixed solvents after being sufficiently mixed, and are added after stirring 20min
Enter catalyst methane sulfonic acid 0.5g, 24h is stirred at reflux at 50 DEG C.After reaction terminates, with ethanol wash products 3 times, then 70
DEG C vacuum drying 12h, obtain hydrophobically modified hydrated SiO 2.Hydrophobically modified water is added into the reactor with heat-exchanger rig
Silica 6g, PPA 8.9g and isopropanol 20.0g are closed, nitrogen is passed through and stirs, 500mg/L catalyst chlorine is added after 5min
Platinic acid 4.2mL, 8h is stirred at reflux at 40 DEG C.After reaction terminates, washed again with ethanol 1 time for 2 times with isopropanol wash products,
24h is dried at 120 DEG C, that is, obtains final products SiO2@PPA.(wherein alkali content is in 100mL ternary composite flooding water extractions
700mg/L, surface-active contents are 300mg/L, and polymer content is 500mg/L) add 2.0g/LSiO2@PPA are mixed,
1h is vibrated at 30 DEG C.The oil-polluted water oil-water interfaces handled by support type reverse-phase emulsifier are clear, and water colour is clear, and de-oiling rate is
92.3%.
Embodiment 3：After the 5.6g of ether epoxy -1, the 16.3g of methyl ether -1 are mixed with containing hydrogen silicone oil 20.0g, add
500mg/L catalyst chloroplatinic acid 3.4mL, stirring 20min is placed in microwave reactor, and 20min is reacted under microwave power 200W,
Reaction product n-hexane fully dissolves, and isolates after undissolved product, and revolving removes a small amount of solvent, then vacuum is done at 60 DEG C
Dry 24h, obtains co-modified silicone oil intermediate.Dibutyl amine 15.0g and second two are sequentially added into the reactor with heat-exchanger rig
Amine crosslinker 1.1g, is passed through nitrogen and stirs, and epoxychloropropane 10.3g is added at 30 DEG C, adds the 1h to 60 that heated up after end
DEG C, continue stirring reaction 6h, yellow viscous liquid product is obtained after cooling, product is used 1:1 absolute ethyl alcohol-acetone is fully washed
Afterwards, revolving removes solvent, is dried in vacuo 24h at 70 DEG C, obtains polyquaternium.Into the reactor with heat-exchanger rig successively
Polyquaternium 8.33g and isopropanol 15.0g is added, nitrogen is passed through and stirs, co-modified silicone oil 10g is added at 35 DEG C, is stirred
5h is reacted, product uses 1 after cooling:1 absolute ethyl alcohol-acetone soln is washed three times, and revolving is dried in vacuo 24h after removing solvent, i.e.,
Obtain polyethers polyquaternium reverse-phase emulsifier (PPA).Granular hydrated silica by particle size distribution range at 50 μm~100 μm
10.0g and silane coupler 20.0g are added in 100g ethanol-water mixed solvent after being sufficiently mixed, and are added after stirring 20min
Catalyst methane sulfonic acid 0.5g, 24h is stirred at reflux at 50 DEG C.After reaction terminates, with ethanol wash products 3 times, then at 70 DEG C
12h is dried in vacuo, hydrophobically modified hydrated SiO 2 is obtained.Hydrophobically modified hydration is added into the reactor with heat-exchanger rig
Silica 6g, PPA 8.9g and isopropanol 20.0g, are passed through nitrogen and stir, and 500mg/L catalyst chlorine platinum is added after 5min
Sour 4.2mL, 8h is stirred at reflux at 40 DEG C.After reaction terminates, washed 1 time with isopropanol wash products 2 times, then with ethanol,
24h is dried at 120 DEG C, that is, obtains final products SiO2@PPA.(wherein alkali content is in 100mL ternary composite flooding water extractions
700mg/L, surface-active contents are 300mg/L, and polymer content is 500mg/L) add 2.0g/LSiO2@PPA are mixed,
30 times vibration 1h.The oil-polluted water oil-water interfaces handled by support type reverse-phase emulsifier are clear, and water colour is clear, and de-oiling rate is
90.6%.
Embodiment 4：After the 12.4g of ether epoxy -2, the 4.2g of methyl ether -1 are mixed with containing hydrogen silicone oil 15.0g, add
500mg/L catalyst chloroplatinic acid 2.6mL, stirring 20min is placed in microwave reactor, and 20min is reacted under microwave power 200W,
Reaction product n-hexane fully dissolves, and isolates after undissolved product, and revolving removes a small amount of solvent, then vacuum is done at 60 DEG C
Dry 24h, obtains co-modified silicone oil intermediate.Dibutyl amine 19.0g and many second are sequentially added into the reactor with heat-exchanger rig
Alkene polyamine crosslinkers 0.3g, is passed through nitrogen and stirs, and epoxychloropropane 10.3g is added at 30 DEG C, adds the 1h that heated up after end
To 60 DEG C, continue stirring reaction 6h, obtain yellow viscous liquid after cooling, product is used 1:1 absolute ethyl alcohol-acetone is fully washed
Afterwards, revolving removes solvent, then is dried in vacuo 24h at 70 DEG C, obtains polyquaternium.Into the reactor with heat-exchanger rig according to
Secondary addition polyquaternium 8.33g and isopropanol 15.0g, is passed through nitrogen and stirs, co-modified silicone oil 10g is added at 35 DEG C, is stirred
Reaction 5h is mixed, product uses 1 after cooling:1 absolute ethyl alcohol-acetone soln is washed three times, and revolving is dried in vacuo 24h after removing solvent,
Obtain polyethers polyquaternium reverse-phase emulsifier (PPA).Hydrated SiO 2 by particle size distribution range at 10 μm~50 μm
Grain 10.0g and silane coupler 20.0g is added in 100g ethanol-water mixed solvents after being sufficiently mixed, and is added after stirring 20min
Catalyst methane sulfonic acid 0.5g, 24h is stirred at reflux at 40 DEG C.After reaction terminates, with ethanol wash products 3 times, then at 70 DEG C
12h is dried in vacuo, hydrophobically modified hydrated SiO 2 is obtained.Hydrophobically modified hydration is added into the reactor with heat-exchanger rig
Silica 6g, PPA 8.9g and isopropanol 20.0g, are passed through nitrogen and stir, and 500mg/L catalyst chlorine platinum is added after 5min
Sour 4.2mL, 8h is stirred at reflux at 40 DEG C.After reaction terminates, washed 1 time with isopropanol wash products 2 times, then with ethanol,
24h is dried at 120 DEG C, that is, obtains final products SiO2@PPA.(wherein alkali content is in 100mL ternary composite flooding water extractions
700mg/L, surface-active contents are 300mg/L, and polymer content is 500mg/L) add 1.5g/LSiO2@PPA are mixed,
1h is vibrated at 30 DEG C.The oil-polluted water oil-water interfaces handled by support type reverse-phase emulsifier are clear, and water colour is clear, and de-oiling rate is
91.6%.
Fig. 7 is ternary composite flooding water extraction treatment effect comparison diagram.Wherein left figure is the ternary that oil concentration is 500mg/L
Composite-driven produced water sample, right figure is through SiO2Water sample after@PPA processing.
Embodiment 5：After the 8.4g of ether epoxy -1, the 8.6g of methyl ether -2 are mixed with containing hydrogen silicone oil 13.0g, 500mg/ is added
L catalyst chloroplatinic acid 2.6mL, stirring 20min is placed in microwave reactor, is reacted 20min under microwave power 200W, will be reacted
Product n-hexane fully dissolves, and isolates after undissolved product, and revolving removes a small amount of solvent, then is dried in vacuo at 60 DEG C
24h, obtains co-modified silicone oil intermediate.Dibutyl amine 19.0g and dibutyl amine are sequentially added into the reactor with heat-exchanger rig
Crosslinking agent 0.5g, is passed through nitrogen and stirs, and epoxychloropropane 10.3g is added at 30 DEG C, adds and is heated up 1h to 60 DEG C after end,
Continue stirring reaction 6h, yellow viscous liquid product is obtained after cooling, product is used 1:After 1 absolute ethyl alcohol-acetone is fully washed,
Revolving removes solvent, then is dried in vacuo 24h at 70 DEG C, obtains polyquaternium；Into the reactor with heat-exchanger rig successively
Polyquaternium 8.33g and isopropanol 15.0g is added, nitrogen is passed through and stirs, co-modified silicone oil 10g is added at 35 DEG C, is stirred
5h is reacted, product uses 1 after cooling:1 absolute ethyl alcohol-acetone soln is washed three times, and revolving is dried in vacuo 24h after removing solvent, i.e.,
Obtain polyethers polyquaternium reverse-phase emulsifier (PPA).Granular hydrated silica by particle size distribution range at 10 μm~50 μm
10.0g and silane coupler 20.0g are added in 100g ethanol-water mixed solvents after being sufficiently mixed, and are added and are urged after stirring 20min
Agent Loprazolam 0.5g, 24h is stirred at reflux at 50 DEG C.After reaction terminates, with ethanol wash products 3 times, then at 70 DEG C
12h is dried in vacuo, hydrophobically modified hydrated SiO 2 is obtained.Hydrophobically modified hydration is added into the reactor with heat-exchanger rig
Silica 6g, PPA 8.9g and isopropanol 20.0g, are passed through nitrogen and stir, and 500mg/L catalyst chlorine platinum is added after 5min
Sour 4.2mL, 8h is stirred at reflux at 40 DEG C.After reaction terminates, washed 1 time with isopropanol wash products 2 times, then with ethanol,
24h is dried at 120 DEG C, that is, obtains final products SiO2@PPA.(wherein alkali content is in 100mL ternary composite flooding water extractions
700mg/L, surface-active contents are 300mg/L, and polymer content is 500mg/L) add 1.5g/LSiO2@PPA are mixed,
1h is vibrated at 30 DEG C.The oil-polluted water oil-water interfaces handled by support type reverse-phase emulsifier are clear, and water colour is clear, and de-oiling rate is
89.8%.
It should be appreciated that for those of ordinary skills, can according to the above description be improved or converted,
And all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (8)
1. a kind of ternary composite flooding water extraction support type reverse-phase emulsifier, it is characterized in that：The structural formula of support type reverse-phase emulsifier
It is as follows：
Wherein, x1=1~30；x2=1~30；x3=1~20；Y=1~50；A=7~19；B=1~19；M=9~10；N=
1~3.
2. a kind of preparation method of ternary composite flooding water extraction support type reverse-phase emulsifier described in claim 1, it is characterized in that：
The preparation method of support type reverse-phase emulsifier：Reverse-phase emulsifier basic framework is synthesized by hydrosilylation first, then will
Polyquaternium carries out epoxy additionization reaction synthesizing polyether polyquaternium reverse-phase emulsifier with co-modified silicone oil, then even using silane
Join agent KH-570 to hydrated SiO 2 (SiO2·nH2O) surface carries out hydrophobically modified, finally that polyethers polyquaternium is anti-phase broken
Emulsion and modified hydrated SiO 2 carry out surface scion grafting polymerisation, prepare support type reverse-phase emulsifier.
3. a kind of preparation method of ternary composite flooding water extraction support type reverse-phase emulsifier according to claim 2, it is special
Levying is：Comprise the following steps that：
1) the basic framework synthesis of rp demulsification agent molecule
After ether epoxy, methyl ether are mixed with containing hydrogen silicone oil, catalyst chloroplatinic acid is added, stirring 20min~30min is placed in micro-
In ripple reactor, 10min~40min is reacted under microwave power 100W~500W, reaction product n-hexane fully dissolves, point
Separate out after undissolved product, revolving removes a small amount of solvent, then is dried in vacuo 24h at 60 DEG C, obtains ether epoxy methyl ether and changes altogether
Property silicone oil intermediate；
2) polyquaternium is synthesized
Dibutyl amine and organic amine crosslinking agent are sequentially added in the reactor with condensing unit, nitrogen is passed through and stirs,
Epoxychloropropane is slowly added at 10 DEG C~30 DEG C, is heated up 1h to 40 DEG C~80 DEG C after the completion of adding, continuation stirring reaction 3~
8h, cooling obtains yellow viscous liquid product, and reaction product is used into 1:Revolving removes molten after 1 absolute ethyl alcohol-acetone is fully washed
Agent, then 24h is dried in vacuo at 70 DEG C, obtain product polyquaternium；
3) polyethers polyquarternium-type reverse-phase emulsifier is synthesized
Polyquaternium and alcohols solvent are sequentially added into the reactor with condensing unit, nitrogen is passed through and stirs, at 25 DEG C
Add co-modified silicone oil at~45 DEG C, 3~7h of stirring reaction, after cooling, product uses 1:1 absolute ethyl alcohol-acetone soln is repeatedly washed
Wash, revolving removes solvent, be dried in vacuo 24h, as products therefrom polyethers polyquaternium PPA；
4) hydrophobically modified of carrier hydrated SiO 2
It is added in alcohols solvent, adds after stirring 20min~30min after hydrated SiO 2 and silane coupler are sufficiently mixed
Enter catalyst methane sulfonic acid, 16h~32h is stirred at reflux at 35 DEG C~60 DEG C, after reaction terminates, with ethanol wash products 3~5
It is secondary, 12h~14h is dried in vacuo at 70 DEG C~90 DEG C, hydrophobically modified hydrated SiO 2 is obtained；
5) synthesis of support type reverse-phase emulsifier
Hydrophobically modified hydrated SiO 2, polyethers polyquaternium PPA and alcohols are added into the reactor with heat-exchanger rig molten
Agent, is passed through nitrogen and stirs, and catalyst chloroplatinic acid is added after 5min, and 6h~10h, reaction knot are stirred at reflux at 30 DEG C~50 DEG C
Shu Hou, is successively repeatedly washed with isopropanol, ethanol, then dries 24h at 120 DEG C, that is, obtains final products SiO2@PPA。
4. a kind of preparation method of ternary composite flooding water extraction support type reverse-phase emulsifier according to claim 3, it is special
Levying is：Preparation process 1) in add ether epoxy be allyl polyethenoxy polyoxypropylene epoxy radicals ether -1, EO:PO=10:1、
Allyl polyethenoxy polyoxypropylene epoxy radicals ether -2, EO:PO=3:1；The methyl ether of addition is allyl polyethenoxy polyoxy
Propylene methyl ether -1, EO:PO=1:1st, allyl polyethenoxy polyoxypropylene methyl ether -2, EO:PO=7:1；Described is hydrogeneous
The hydrogeneous mass percent amount of silicone oil is 0.1%~0.25%；The ether epoxy and methyl ether mol ratio 1:5~5:1, si-h bond
Mol ratio with carbon-carbon double bond is 1:1.0~1:1.2, catalyst chloroplatinic acid consumption is the μ g/g of 10 μ g/g~50.
5. a kind of preparation method of ternary composite flooding water extraction support type reverse-phase emulsifier according to claim 3, it is special
Levying is：Preparation process 2) described in epoxychloropropane and dibutyl amine mol ratio be 1:0.9~1:1.4；The organic amine crosslinking
Agent is ethylenediamine, n-butylamine, polyethylene polyamine, and organic amine dosage is the 1%~15% of reactant quality percentage.
6. a kind of preparation method of ternary composite flooding water extraction support type reverse-phase emulsifier according to claim 3, it is special
Levying is：Preparation process 3) described in alcohols solvent be methanol, ethanol or isopropanol；Described polyquaternium, co-modified silicone oil, alcohol
The mass ratio of class solvent is 0.8~1.2:0.5~2.5:15~30.
7. a kind of preparation method of ternary composite flooding water extraction support type reverse-phase emulsifier according to claim 3, it is special
Levying is：Preparation process 4) described in silane coupler be 3- methacryloxypropyl trimethoxy silanes；Described alcohol
Class solvent is methanol, ethanol or isopropanol, and the mass ratio of the alcohols solvent, water and Loprazolam is 1:1:0.03~0.07；
Described granular hydrated silica particle size distribution range is 10~100 μm, hydrated SiO 2 and silane coupler mass ratio
For 0.8~1.2:2.0~10.0.
8. a kind of preparation method of ternary composite flooding water extraction support type reverse-phase emulsifier according to claim 3, it is special
Levying is：Preparation process 5) described in alcohols solvent be methanol, ethanol or isopropanol；Hydrophobically modified silica, polyethers polyquaternary amine
Salt PPA is 0.6~0.8 with alcohols solvent mass ratio:0.8~1.2:2.0~3.0；Catalyst chloroplatinic acid consumption be 40 μ g/g~
80μg/g。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109054888A (en) * | 2018-07-26 | 2018-12-21 | 中国石油天然气集团有限公司 | A kind of demulsifier and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2043751A2 (en) * | 2006-06-22 | 2009-04-08 | Momentive Performance Materials Inc. | Method for demulsifying |
| CN103936185A (en) * | 2013-06-04 | 2014-07-23 | 克拉玛依市三达新技术开发有限责任公司 | Method for treating and reusing super-heavy oil high-temperature sewage in thermal recovery boiler |
| CN105820833A (en) * | 2016-03-30 | 2016-08-03 | 中国海洋石油总公司 | Combined crude oil demulsifying agent and preparation method thereof |
| CN106047397A (en) * | 2016-05-26 | 2016-10-26 | 句容宁武高新技术发展有限公司 | Method for preparing silicon-containing polyether demulsifier |
-
2017
- 2017-06-12 CN CN201710436917.XA patent/CN107162154B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2043751A2 (en) * | 2006-06-22 | 2009-04-08 | Momentive Performance Materials Inc. | Method for demulsifying |
| CN103936185A (en) * | 2013-06-04 | 2014-07-23 | 克拉玛依市三达新技术开发有限责任公司 | Method for treating and reusing super-heavy oil high-temperature sewage in thermal recovery boiler |
| CN105820833A (en) * | 2016-03-30 | 2016-08-03 | 中国海洋石油总公司 | Combined crude oil demulsifying agent and preparation method thereof |
| CN106047397A (en) * | 2016-05-26 | 2016-10-26 | 句容宁武高新技术发展有限公司 | Method for preparing silicon-containing polyether demulsifier |
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| CN109054888A (en) * | 2018-07-26 | 2018-12-21 | 中国石油天然气集团有限公司 | A kind of demulsifier and preparation method thereof |
| CN109054888B (en) * | 2018-07-26 | 2021-01-01 | 中国石油天然气集团有限公司 | Demulsifier and preparation method thereof |
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