CN110041474A - A kind of hybrid cation reverse-phase emulsifier and the preparation method and application thereof - Google Patents
A kind of hybrid cation reverse-phase emulsifier and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of hybrid cation reverse-phase emulsifiers and the preparation method and application thereof.The preparation method of the hybrid cation reverse-phase emulsifier includes the following steps: 1) using silane coupling agent to Nano-meter SiO_22It carries out conducting modification of surface hydroxy group and obtains modified Nano SiO2, modified Nano SiO2Face extremities connect carbon-carbon double bond；2) modified Nano SiO2, acrylamide and dimethyl diallyl ammonium chloride carry out ternary polymerization and react to obtain the final product.The present invention is used containing unsaturated double bond silane coupling agent to Nano-meter SiO_22It is modified, Nano-meter SiO_2 after modified2With certain hydrophobicity, end has unsaturated carbon-carbon double bond, it can be by carrying out ternary polymerization with AM and DMDAAC, a kind of reticular structure of hydrophilic soft shell of hydrophobic stone is formed, this structure can effectively improve charge density, on the basis of guaranteeing low cationic degree, realize effectively demulsification, and by the demulsifier of the wanted compatibility of this reverse-phase emulsifier be it is non-ionic, form that floc strength is low, and de-oiling rate is high.
Description
Technical field
The present invention relates to a kind of hybrid cation reverse-phase emulsifiers and the preparation method and application thereof, belong to stone
Oily chemical field.
Background technique
With the extensive use of tertiary oil recovery technology polymer flooding, crude oil water emulsification degree is higher and higher, and demulsification difficulty is cured
Increasing, on the basis of guarantee demulsifier low dosage, causing demulsification to deviate from water, oil content is higher and higher, and this requires mention
For it is a kind of can with demulsifier compound and the medicament of oil content in demulsification abjection water, i.e. reverse-phase emulsifier is effectively reduced.According to phase
Literature survey is closed it is found that conventional inverter demulsifier is mainly based on cation, reason is that oil droplets with negative electrical charge, are led to
Charge neutralization is crossed, medicament can be made to combine with oil droplet, and then oil-water interfaces layer tension is effectively reduced, it is final to realize that demulsification is clear
Water, but the problem is that cationic degree is excessively high, greasy filth coagulation easy to form.Therefore need to provide a kind of reverse phase of low cationic degree
Demulsifier.
Summary of the invention
The object of the present invention is to provide a kind of hybrid cation reverse-phase emulsifier and preparation method thereof with answer
With the present invention passes through silane coupling agent (γ-methacryloxypropyl trimethoxy silane (KH570)) to end hydroxyl first
The Nano-meter SiO_2 of base2Be modified, make its end with double bond, then with acrylamide (AM) and dimethyl diallyl chlorination
Ammonium (DMDAAC) carries out ternary polymerization, finally obtains a kind of reticular structure of hydrophilic soft shell of hydrophobic stone；Provided organic/nothing
Machine hybrid cation reverse-phase emulsifier has fast emulsion breaking, de-oiling efficiency high and generates the characteristic of more low intensive oily wadding body.
The preparation method of hybrid cation reverse-phase emulsifier provided by the present invention, includes the following steps:
1) using silane coupling agent to Nano-meter SiO_22It carries out conducting modification of surface hydroxy group and obtains modified Nano SiO2, the modification receives
Rice SiO2Face extremities connect carbon-carbon double bond；
2) the modified Nano SiO2, acrylamide and dimethyl diallyl ammonium chloride carry out ternary polymerization and react, i.e.,
Obtain the hybrid cation reverse-phase emulsifier.
In above-mentioned preparation method, in step 1), the silane coupling agent can be γ-methacryloxypropyl front three
Oxysilane or gamma-aminopropyl-triethoxy-silane；
When the silane coupling agent be γ-methacryloxypropyl trimethoxy silane when, obtain it is described it is organic/
For the structural formula of inorganic hybrid cation reverse-phase emulsifier as shown in formula I, formula II is its corresponding schematic arrangement:
In formula I, a >=1；b≥1；c≥1；
Group shown in R ' expression III:
In formula II, blue circle expression nano silica, 8 branching representation silane coupling agents being connected on blue circle,
The curve being connected in branch indicates polymer.
In above-mentioned preparation method, in step 1), using Nano-meter SiO_2 described in the Compound mixed solution of ethyl alcohol and water2Solution,
And adopt and be adjusted with acid its pH value to 1~6, the silane coupling agent is added to the Nano-meter SiO_22Solution in；
The volume ratio of the water and the ethyl alcohol can be 0.5~5:1, preferably 1~3:1；
PH value preferable 3~5；
Prepare the Nano-meter SiO_22Solution can carry out as steps described below: using ultrasound by the Nano-meter SiO_22Uniformly divide
It dissipates in the mixed liquor of the ethyl alcohol and water, and pH value is adjusted to 1~6,10~40min's using the HCl solution of 2mol/L
During, it is placed in magnetic stirrer 1min every 5min, finally obtains evenly dispersed Nano-meter SiO_22Solution；
The mole dosage of the silane coupling agent is the Nano-meter SiO_221~30 times of surface hydroxyl amount, preferably 4~20 times
Or 10 times；
The Nano-meter SiO_22The quantity of surface hydroxyl can be measured as steps described below:
By the Nano-meter SiO_2 of a certain amount of (Wg)2Solid powder is placed in 100ml conical flask, using the NaOH of 0.05mol/L
Solution 80mL is stirred for 24 hours under air-proof condition, is well-dispersed in it in aqueous slkali, is centrifuged to obtain CmL solution (≈ 80mL), from point
From CmL solution in measure 10mL, then neutrality is titrated to using the HCl solution of 0.05mol/L, HCl solution consumption remembers A ml；
Finally surplus solution (C-10) mL is titrated using HCl solution, HCl solution consumption remembers B ml, finally according to formula:Nano-meter SiO_2 is finally calculated2The content of surface hydroxyl.
In above-mentioned preparation method, in step 1), the temperature of the conducting modification of surface hydroxy group can be 30~100 DEG C, preferably 40
~80 DEG C, the time can be 0.5~10h, preferably 3~8h；
After the conducting modification of surface hydroxy group, isolated and purified after being dispersed using ethyl alcohol: be added ethyl alcohol dispersion after from
Under 7000~12000rmp/min of scheming revolving speed × 5min, centrifuge separation, ethyl alcohol redisperse is iteratively repeated 2~6 times.
In above-mentioned preparation method, in step 2), the modified Nano SiO2Dosage be the acrylamide with it is described
The 0.1~5% of dimethyl diallyl ammonium chloride gross mass, concretely 0.1~2%；
The mass ratio of the acrylamide and the dimethyl diallyl ammonium chloride can be 0.1~5:1, concretely
0.1~2:1；
The solvent that the ternary polymerization reaction uses is at least one of water, ethyl alcohol, methanol and toluene.
In above-mentioned preparation method, in step 2), the temperature of the ternary polymerization reaction is 20~90 DEG C, the time 0.5
~10h.
In above-mentioned preparation method, in step 2), the ternary polymerization reaction causes system using water soluble, redox；
In the water soluble, redox initiation system, oxidant is hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, over cure
At least one of sour potassium and hydroperoxides, reducing agent are inorganic reducing agent or organic reducing agent；
The inorganic reducing agent is Fe2+、Cu+、NaHSO3And Na2SO3At least one of；
The organic reducing agent is at least one of tetramethylethylenediamine, oxalic acid and alcohol；
Reduction after 1~6 initial oxidation is divided to sequentially add the water soluble, redox initiation system；
The dosage that the water soluble, redox causes system is the acrylamide and the dimethyl diallyl chlorine
Change the 0~1% of ammonium gross mass, but is not zero；
The molar ratio of the oxidant and the reducing agent is 1:1；
The ternary polymerization reaction carries out under nitrogen protection.
System after ternary polymerization reaction is poured slowly into etoh solvent, acetone and/or anhydrous ether, is sunk
Analysis, drying and grinding, the final crude product for obtaining hybrid cation reverse-phase emulsifier (PNAD).
The hybrid cation reverse-phase emulsifier of the method for the present invention preparation can be used for handling oily wastewater
Carry out deoiling treatment.
(it is (de- to sequentially add demulsifier when hybrid cation reverse-phase emulsifier of the present invention and demulsifier compound
Water) and reverse-phase emulsifier (clear water), it can be used for handling water-in-oil emulsion, clear water processing can be carried out.
The demulsifier can be non-ionic demulsifier conventional in the art, such as phenol-amine resin polyether type demulsifying agent.
The dosage of the demulsifier is 100mg/L, and the dosage of the hybrid cation reverse-phase emulsifier is
150~500mg/L.
The present invention is used containing unsaturated double bond silane coupling agent to Nano-meter SiO_22It is modified, Nano-meter SiO_2 after modified2Have
Certain hydrophobicity, end have unsaturated carbon-carbon double bond, can form a kind of dredge by carrying out ternary polymerization with AM and DMDAAC
The reticular structure of the hydrophilic soft shell of hydraulic core, this structure can effectively improve charge density, on the basis of guaranteeing low cationic degree,
Realize effectively demulsification, and by the demulsifier of the wanted compatibility of this reverse-phase emulsifier be it is non-ionic, formation floc strength it is low, de-oiling
Rate is high.The preparation method of reverse-phase emulsifier of the present invention has the advantage that preparation process is simple and raw material is cheap, is very suitable for industry
Change application.
Detailed description of the invention
Fig. 1 is the compounding clear water effect picture that reverse-phase emulsifier PNAD-1/2/3 of the present invention is used alone.
Fig. 2 is the clear water effect picture that reverse-phase emulsifier PNAD-1/2/3 of the present invention is compounded with demulsifier A.
Fig. 3 is the dehydration rate figure that reverse-phase emulsifier PNAD-1/2/3 of the present invention is compounded with demulsifier A.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Dehydration rate is obtained by having the measurement of colour tube method in following embodiments, and dehydration rate takes off after being equal to addition demulsifier A
The ratio between water yield and former emulsion total moisture content.
Demulsifier A is phenol-amine resin polyether type demulsifying agent in following embodiments, is prepared as follows:
Quantitative bisphenol-A (bis-phenol base propane) is uniformly mixed with the tetraethylenepentamine of 4 times of bisphenol-A moles, is heated
It is allowed to be completely dissolved to 150 DEG C or so, is cooled to 50 DEG C, the formalin with tetraethylenepentamine equimolar amounts is added dropwise, keep temperature
50 DEG C of degree, is added dropwise rear insulation reaction 2h.A certain amount of dimethylbenzene is added, is warming up to 100~110 DEG C, back flow reaction 2h.It is slow
Slow heating under reflux conditions takes water out of, after water base steams, material is under vacuum-pumping conditions steamed dimethylbenzene, i.e.,
Obtain phenol-amine resin initiator.
Above-mentioned initiator and catalyst KOH are added to autoclave and started to warm up, it is true with vacuum pumping under room temperature
To gauge pressure in -0.1MPa or so, nitrogen purging displacement vacuumizes 30min, at 120 ± 5 DEG C, starts to be intermittently added PO, anti-sky
Answer the control of kettle pressure in 0.2~0.4MPa.After charging, when the pressure of reaction kettle is fallen after rise, continuation is reacted at such a temperature
Until -0.05MPa when being reduced to beginning, thinks fully reacting at this time, oleophylic head is made.Oleophylic head is reacted with KOH investment
Kettle, it is consistent with oleophylic head step is prepared to be warming up to 120 ± 5 DEG C, it is intermittently added EO, pressure controls 0.2~0.4MPa, fed
Bi Hou continues to react-the 0.05MPa until when being reduced to beginning at such a temperature, recognize at this time when the pressure of reaction kettle is fallen after rise
For fully reacting, block polyether is made, as shown in Equation 1:
Block polyether and dimethylbenzene (mass concentration for guaranteeing dimethylbenzene after completion of the reaction is 50%) are added to equipped with machine
In the there-necked flask of tool stirring, 55 DEG C are heated to oil bath pan.Using constant pressure funnel, it is fixed to be slowly added dropwise into there-necked flask
Xylene solution, the constant temperature for measuring 10%PM-200 (poly methylene poly phenyl poly isocyanate), after being added dropwise, are warming up to 65 DEG C
1h is reacted, the demulsifier A that concentration is 50% can be obtained.
Embodiment 1, hybrid cation reverse-phase emulsifier PNAD-1 preparation
(1) 2g Nano-meter SiO_2 is weighed2In 100ml conical flask, using the NaOH solution 80ml of 0.05mol/L in sealing strip
It is stirred under part for 24 hours, is well-dispersed in it in aqueous slkali, be centrifuged to obtain C ml solution, (≈ 80mL), from isolated CmL solution
10mL is measured, then the C solution of 10ml is carried out to be titrated to neutrality using the HCl of 0.05mol/L, HCl solution consumption remembers A ml,
Finally surplus solution (C-10) mL is titrated using HCl solution, HCl solution consumption remembers B ml, finally according to formula:Silicone hydroxyl surface concentrations 5.35mmol/g is finally calculated；
(2) using ultrasonic by 5g Nano-meter SiO_22It is dispersed in the mixed solvent 70ml (V of ethyl alcohol and water(water/ethyl alcohol)=3) in,
And pH to 4 is adjusted using the HCl solution of 2mol/L, during which time 30min is placed in magnetic stirrer 1min every 5min,
Finally obtain evenly dispersed Nano-meter SiO_22Solution 70ml, wherein Nano-meter SiO_2 containing 5g2；
(3) by the resulting evenly dispersed Nano-meter SiO_2 of step (2)2Solution is placed in 250ml three-necked flask, by silane idol
Join agent KH570 according to SiO2The ratio of surface hydroxyl quantity molar ratio 10:1 is added 62.69g, at the uniform velocity and is slowly added dropwise to
In reaction flask, at 50 °C, reaction time 4h again obtains modified Nano SiO2Crude product；
(4) by the resulting modified Nano SiO of step (3)2Crude product after being cooled to room temperature, is rinsed using 10ml ethyl alcohol
Reaction flask inner wall, then pour into centrifuge tube, at centrifuge speed 8000rmp/min × 5min, centrifuge separation, ethyl alcohol divides again
It dissipates, is iteratively repeated 3 times, final separation obtains modified Nano SiO after purification2Solution, wherein modified Nano SiO2Content 4.5g；
(5) the resulting modified Nano SiO of 0.5g step (4) is taken2, water ultrasonic disperse；Weigh 6.94g monomer AM and
13.79g DMDAA；Reaction solution is uniformly mixed, is placed in oil bath pan, temperature is at 30 DEG C, reaction time 0.5h；N2Protection divides 3
Reduction sequentially adds initiator after secondary initial oxidation；
(6) synthesis of this polymer is to cause system using water soluble, redox, weighs 1.2498g initiator, wherein
Oxidant selects ammonium persulfate；Reducing agent is then organic reducing agent tetramethylethylenediamine, and the molar ratio of the two is 1:1；
(7) it by 57.16g terpolymer PNAD solution obtained by step (5), is poured slowly into etoh solvent, carries out precipitating,
Drying and grinding, it is final to obtain 38.79g polymer P NAD-1.
By hybrid cation reverse-phase emulsifier PNAD-1 manufactured in the present embodiment be applied to oily wastewater and with
The research of demulsifier A composite usage emulsion of crude oil, steps are as follows:
(1) it takes 5ml oily wastewater in 10ml centrifuge tube, is separately added into 0.075ml, 0.10ml, 0.125ml and 0.15ml
Polymer P NAD-1 solution (its additional amount is respectively 150mg/L, 200mg/L, 250mg/L, 300mg/L), in 3000rmp/min
Oscillator vibrated, be subsequently placed at 70 DEG C of water bath with thermostatic control 1h；Through the pure hexane of high performance liquid chromatography to the sewage after demulsification
Oily extraction is carried out, by oil content in oil content Instrument measuring water in the portable water of U.S. Tener TD-500D, respectively
9287mg/L, 7245mg/L, 5713mg/L and 2444mg/L, by calculating, de-oiling rate respectively reaches 53.57%, 63.78%,
71.44% and 87.78%.
Clear water effect picture using 0.15ml polymer P NAD-1 solution is as shown in Figure 1.
(2) it takes 30ml oily wastewater and 30ml emulsion of crude oil to have in plug centrifuge tube in 100ml, 0.6ml demulsification is first added
Agent A (its additional amount is 100mg/L), is then respectively adding 0.9ml, 1.2ml, 1.5m and 1.8ml polymer P NAD-1 solution (its
Additional amount is respectively 150mg/L, 200mg/L, 250mg/L, 300mg/L), it shakes in the shaking table oscillator of 800rmp/min
It swings, is subsequently placed at 70 DEG C of water bath with thermostatic control 1h；Visually read abjection water volume, calculate dehydration rate respectively reach 94%,
81.2%, 85% and 83%；Oily extraction is carried out to the sewage after demulsification through the pure hexane of high performance liquid chromatography, passes through U.S. Tener
Oil content, respectively 5879,3465,1987 and 2444mg/L, clear water in oil content Instrument measuring water in the portable water of TD-500D
Shown in such as Fig. 2 (a) of effect picture afterwards, shown in dehydration rate such as Fig. 3 (a).
Embodiment 2, hybrid cation reverse-phase emulsifier PNAD-2 preparation
(1) 2g Nano-meter SiO_2 is weighed2In 100ml conical flask, using the NaOH solution 80ml of 0.05mol/L in sealing strip
It is stirred under part for 24 hours, is well-dispersed in it in aqueous slkali, be centrifuged to obtain C ml solution, then use the HCl of 0.05mol/L to 10ml
C solution be titrated to neutrality, consumption is remembered A ml, is finally titrated using HCl solution to (C-10) ml solution, consumption
Amount note B ml, finally according to formula:Silicone hydroxyl surface concentrations 5.25mmol/g is finally calculated；
(2) using ultrasonic by 5g Nano-meter SiO_22It is dispersed in the mixed solvent 70ml (V of ethyl alcohol and water(water/ethyl alcohol)=3) in,
And pH to 4 is adjusted using the HCl solution of 2mol/L, during which time 30min is placed in magnetic stirrer 1min every 5min,
Finally obtain evenly dispersed Nano-meter SiO_22Solution 70ml, wherein Nano-meter SiO_2 containing 5g2；
(3) by the resulting evenly dispersed Nano-meter SiO_2 of step (2)2Solution is placed in 250ml three-necked flask, by silane idol
Join agent KH570 according to SiO2The ratio of surface hydroxyl quantity molar ratio 10:1 is added 62.69g, at the uniform velocity and is slowly added dropwise to
In reaction flask, at 50 °C, reaction time 4h again obtains modified Nano SiO2Crude product；
(4) by the resulting modified Nano SiO of step (3)2Crude product after being cooled to room temperature, is rinsed using 10ml ethyl alcohol
Reaction flask inner wall, then pour into centrifuge tube, at centrifuge speed 8000rmp/min × 5min, centrifuge separation, ethyl alcohol divides again
It dissipates, is iteratively repeated 3 times, final separation obtains modified Nano SiO after purification2Solution, wherein modified Nano SiO2Content 4.5g；
(5) the resulting modified Nano SiO of 0.5g step (4) is taken2, water ultrasonic disperse；Weigh 5.21g monomer AM and
15.62g DMDAAC；Reaction solution is uniformly mixed, is placed in oil bath pan, temperature is at 30 DEG C, reaction time 0.5h；N2Protection, point
Reduction sequentially adds initiator after 3 initial oxidations；
(6) synthesis of this polymer is to cause system using water soluble, redox, weighs 1.2498g initiator, wherein
Oxidant selects ammonium persulfate；Reducing agent is then organic reducing agent tetramethylethylenediamine；
(7) it by 57.16g terpolymer PNAD solution obtained by step (5), is poured slowly into etoh solvent, carries out precipitating,
Drying and grinding, it is final to obtain 34.30g polymer P NAD-2.
By above-mentioned hybrid cation reverse-phase emulsifier PNAD-2 be applied to oily wastewater and with demulsifier A
The research of composite usage emulsion of crude oil, steps are as follows:
(1) it takes 5ml oily wastewater in 10ml centrifuge tube, is separately added into 0.075ml, 0.10ml, 0.125ml and 0.15ml
Polymer P NAD-2 solution (its additional amount is respectively 150mg/L, 200mg/L, 250mg/L, 300mg/L), in 3000rmp/min
Oscillator vibrated, be subsequently placed at 70 DEG C of water bath with thermostatic control 1h；Through the pure hexane of high performance liquid chromatography to the sewage after demulsification
Oily extraction is carried out, by oil content in oil content Instrument measuring water in the portable water of U.S. Tener TD-500D, respectively
13257mg/L, 8029mg/L, 4394mg/L and 2610mg/L, by calculating, de-oiling rate respectively reaches 33.75%, 59.86%,
78.03% and 86.95%.
Clear water effect picture using 0.15ml polymer P NAD-2 solution is as shown in Figure 1.
(2) it takes 30ml oily wastewater and 30ml emulsion of crude oil to have in plug centrifuge tube in 100ml, 0.6ml demulsification is first added
Agent A (its additional amount is 100mg/L), is then respectively adding 0.9ml, 1.2ml, 1.5m and 1.8ml polymer P NAD-2 solution (its
Additional amount is respectively 150mg/L, 200mg/L, 250mg/L, 300mg/L), polymer P NAD-2 solution and 0.6ml demulsifier
A is vibrated in the shaking table oscillator of 800rmp/min, is subsequently placed at 70 DEG C of water bath with thermostatic control 1h；Visually read abjection water
Volume calculates dehydration rate and respectively reaches 85%, 96%, 92% and 85%；After the pure hexane of high performance liquid chromatography is to demulsification
Sewage carries out oily extraction, by oil content in oil content Instrument measuring water in the portable water of U.S. Tener TD-500D, respectively
6215,3783,1876 and 1444mg/L, shown in effect picture such as Fig. 2 (b) after clear water, shown in dehydration rate such as Fig. 3 (b).
Embodiment 3, hybrid cation reverse-phase emulsifier PNAD-3 preparation
(1) 2g Nano-meter SiO_2 is weighed2In 100ml conical flask, using the NaOH solution 80ml of 0.05mol/L in sealing strip
It is stirred under part for 24 hours, is well-dispersed in it in aqueous slkali, be centrifuged to obtain C ml solution, then use the HCl of 0.05mol/L to 10ml
C solution be titrated to neutrality, consumption is remembered A ml, is finally titrated using HCl solution to (C-10) ml solution, consumption
Amount note B ml, finally according to formula:Silicone hydroxyl surface concentrations 5.35mmol/g is finally calculated；
(2) using ultrasonic by 5g Nano-meter SiO_22It is dispersed in the mixed solvent 70ml (V of ethyl alcohol and water(water/ethyl alcohol)=3) in,
And pH to 4 is adjusted using the HCl solution of 2mol/L, during which time 30min is placed in magnetic stirrer 1min every 5min,
Finally obtain evenly dispersed Nano-meter SiO_22Solution 70ml, wherein Nano-meter SiO_2 containing 5g2；
(3) by the resulting evenly dispersed Nano-meter SiO_2 of step (2)2Solution is placed in 250ml three-necked flask, by silane idol
Join agent KH570 according to SiO2The ratio of surface hydroxyl quantity molar ratio 10:1 is added 62.69g, at the uniform velocity and is slowly added dropwise to
In reaction flask, at 50 °C, reaction time 4h again obtains modified Nano SiO2Crude product；
(4) by the resulting modified Nano SiO of step (3)2Crude product after being cooled to room temperature, is rinsed using 10ml ethyl alcohol
Reaction flask inner wall, then pour into centrifuge tube, at centrifuge speed 8000rmp/min × 5min, centrifuge separation, ethyl alcohol divides again
It dissipates, is iteratively repeated 3 times, final separation obtains modified Nano SiO after purification2Solution, wherein modified Nano SiO2Content 4.5g；
(5) the resulting modified Nano SiO of 0.5g step (4) is taken2, water ultrasonic disperse；Weigh 3.78g monomer AM and
17.04g DMDAAC；Reaction solution is uniformly mixed, is placed in oil bath pan, temperature is at 30 DEG C, reaction time 0.5h；N2Protection, point
Reduction sequentially adds initiator after 3 initial oxidations；
(6) synthesis of this polymer is to cause system using water soluble, redox, weighs 1.2498g initiator, wherein
Oxidant selects ammonium persulfate；Reducing agent is then organic reducing agent tetramethylethylenediamine；
(7) it by 57.16g terpolymer PNAD solution obtained by step (5), is poured slowly into etoh solvent, carries out precipitating,
Drying and grinding, it is final to obtain 38.79g polymer P NAD-3.
By above-mentioned hybrid cation reverse-phase emulsifier PNAD-3 be applied to oily wastewater and with demulsifier A
The research of composite usage emulsion of crude oil, steps are as follows:
(1) it takes 5ml oily wastewater in 10ml centrifuge tube, is separately added into 0.075ml, 0.10ml, 0.125ml and 0.15ml
Polymer P NAD-3 solution (its additional amount is respectively 150mg/L, 200mg/L, 250mg/L, 300mg/L), in 3000rmp/min
Oscillator vibrated, be subsequently placed at 70 DEG C of water bath with thermostatic control 1h；Through the pure hexane of high performance liquid chromatography to the sewage after demulsification
Oily extraction is carried out, by oil content in oil content Instrument measuring water in the portable water of U.S. Tener TD-500D, respectively
13473mg/L, 4733mg/L, 954.1mg/L and 1983mg/L, by calculating, de-oiling rate respectively reaches 32.64%,
76.34%, 95.23% and 90.10%.
Clear water effect picture using 0.15ml polymer P NAD-1 solution is as shown in Figure 1.
(2) it takes 30ml oily wastewater and 30ml emulsion of crude oil to have in plug centrifuge tube in 100ml, 0.6ml demulsification is first added
Agent A (its additional amount is 100mg/L), is then respectively adding 0.9ml, 1.2ml, 1.5m and 1.8ml polymer P NAD-1 solution (its
Additional amount is respectively 150mg/L, 200mg/L, 250mg/L, 300mg/L), it shakes in the shaking table oscillator of 800rmp/min
It swings, is subsequently placed at 70 DEG C of water bath with thermostatic control 1h；Visually read abjection water volume, calculate dehydration rate respectively reach 93.5%,
81.2%, 85% and 81.2%；Oily extraction is carried out to the sewage after demulsification through the pure hexane of high performance liquid chromatography, passes through U.S. spy
Oil content in oil content Instrument measuring water in the portable water of the TD-500D that receives, point be respectively 5119mg/L, 1827mg/L and
1688mg/L and 1766mg/L, shown in effect picture such as Fig. 2 (c) after clear water, shown in dehydration rate such as Fig. 3 (c).
To sum up, de-oiling rate, which is used alone, in reverse-phase emulsifier PNAD-1/2/3 of the present invention can reach 80% or more (300mg/
L)；It also can reach 80% or more with emulsion of crude oil dehydration rate after demulsifier compound, oil content can be down to 1 ‰ left sides in demulsification abjection water
It is right；Offshore platform demulsification can be met to require.
Claims (10)
1. a kind of preparation method of hybrid cation reverse-phase emulsifier, includes the following steps:
1) using silane coupling agent to Nano-meter SiO_22It carries out conducting modification of surface hydroxy group and obtains modified Nano SiO2, the modified Nano
SiO2Face extremities connect carbon-carbon double bond；
2) the modified Nano SiO2, acrylamide and dimethyl diallyl ammonium chloride carry out ternary polymerization and react to get described
Hybrid cation reverse-phase emulsifier.
2. preparation method according to claim 1, it is characterised in that: in step 1), the silane coupling agent is γ-methyl
Acryloyloxypropyltrimethoxysilane or gamma-aminopropyl-triethoxy-silane.
3. preparation method according to claim 1 or 2, it is characterised in that: in step 1), using the mixed liquor of ethyl alcohol and water
Prepare the Nano-meter SiO_22Solution, and adopt and be adjusted with acid its pH value to 1~6, the silane coupling agent is added to described and is received
Rice SiO2Solution in；
The mole dosage of the silane coupling agent is the Nano-meter SiO_221~30 times of surface hydroxyl amount.
4. preparation method according to any one of claim 1-3, it is characterised in that: in step 1), the surface hydroxyl
Modified temperature is 30~100 DEG C, and the time is 0.5~10h；
After the conducting modification of surface hydroxy group, isolated and purified after being dispersed using ethyl alcohol.
5. preparation method described in any one of -4 according to claim 1, it is characterised in that: in step 2), the modified Nano
SiO2Dosage be the 0.1~5% of the acrylamide and the dimethyl diallyl ammonium chloride gross mass；
The mass ratio of the acrylamide and the dimethyl diallyl ammonium chloride is 0.1~5:1；
The solvent that the ternary polymerization reaction uses is at least one of water, ethyl alcohol, methanol and toluene.
6. preparation method according to any one of claims 1-5, it is characterised in that: in step 2), the ternary polymerization
The temperature of reaction is 20~90 DEG C, and the time is 0.5~10h.
7. preparation method according to claim 1 to 6, it is characterised in that: in step 2), the ternary polymerization
Reaction causes system using water soluble, redox；
In the water soluble, redox initiation system, oxidant is hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate
At least one of with hydroperoxides, reducing agent is inorganic reducing agent or organic reducing agent；
The inorganic reducing agent is Fe2+、Cu+、NaHSO3And Na2SO3At least one of；
The organic reducing agent is at least one of tetramethylethylenediamine, oxalic acid and alcohol；
Reduction after 1~6 initial oxidation is divided to sequentially add the water soluble, redox initiation system；
The dosage that the water soluble, redox causes system is the acrylamide and the dimethyl diallyl ammonium chloride
The 0~1% of gross mass, but be not zero；
The molar ratio of the oxidant and the reducing agent is 1:1.
8. the hybrid cation reverse-phase emulsifier of any one of claim 1-7 the method preparation.
9. application of the hybrid cation reverse-phase emulsifier described in claim 8 in processing oily wastewater.
10. application of the hybrid cation reverse-phase emulsifier described in claim 8 in processing water-in-oil emulsion；
The hybrid cation reverse-phase emulsifier and demulsifier compound use.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111018176A (en) * | 2019-12-12 | 2020-04-17 | 陕西欧菲德环保科技有限公司 | Demulsifier, preparation method and application thereof |
| CN111732735A (en) * | 2020-06-11 | 2020-10-02 | 长江大学 | Hyperbranched polymer-SiO2Composite demulsifier and preparation method and application thereof |
| CN112430295A (en) * | 2019-08-26 | 2021-03-02 | 万华化学集团股份有限公司 | Dechlorinating agent, preparation method thereof and application of dechlorinating agent in reducing content and chroma of isocyanate chloride |
| CN113201105A (en) * | 2021-04-12 | 2021-08-03 | 中海油能源发展股份有限公司 | Interface active type core-shell microsphere for oil extraction and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0464957A2 (en) * | 1986-09-08 | 1992-01-08 | Exxon Research And Engineering Company | Hydrophobically functionalized cationic polymers |
| CN102311602A (en) * | 2011-06-07 | 2012-01-11 | 江苏大学 | Acrylate copolymer demulsifier with silica sol in-situ compound core-shell structure and preparation method thereof |
| CN102504144A (en) * | 2011-10-27 | 2012-06-20 | 武汉大学 | Method for preparing nano cationic spherical polyelectrolyte brush |
| CN103525455A (en) * | 2013-10-14 | 2014-01-22 | 江苏大学 | Cationic polymer modified crude oil demulsifying agent |
| CN104531118A (en) * | 2014-12-25 | 2015-04-22 | 郑州正佳能源环保科技有限公司 | Method for preparing intelligent nanometer oil-displacing agent |
| CN107162154A (en) * | 2017-06-12 | 2017-09-15 | 中国矿业大学 | A kind of ternary composite flooding water extraction support type reverse-phase emulsifier and preparation method thereof |
-
2019
- 2019-04-15 CN CN201910298742.XA patent/CN110041474B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0464957A2 (en) * | 1986-09-08 | 1992-01-08 | Exxon Research And Engineering Company | Hydrophobically functionalized cationic polymers |
| CN102311602A (en) * | 2011-06-07 | 2012-01-11 | 江苏大学 | Acrylate copolymer demulsifier with silica sol in-situ compound core-shell structure and preparation method thereof |
| CN102504144A (en) * | 2011-10-27 | 2012-06-20 | 武汉大学 | Method for preparing nano cationic spherical polyelectrolyte brush |
| CN103525455A (en) * | 2013-10-14 | 2014-01-22 | 江苏大学 | Cationic polymer modified crude oil demulsifying agent |
| CN104531118A (en) * | 2014-12-25 | 2015-04-22 | 郑州正佳能源环保科技有限公司 | Method for preparing intelligent nanometer oil-displacing agent |
| CN107162154A (en) * | 2017-06-12 | 2017-09-15 | 中国矿业大学 | A kind of ternary composite flooding water extraction support type reverse-phase emulsifier and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 孙海珠，等: "《纳米粒子与聚合物功能复合材料导论》", 31 March 2015, 东北师范大学出版社 * |
| 朱红，等: "纳米SiO2-聚合物复合破乳剂的研制", 《纳米科技》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112430295A (en) * | 2019-08-26 | 2021-03-02 | 万华化学集团股份有限公司 | Dechlorinating agent, preparation method thereof and application of dechlorinating agent in reducing content and chroma of isocyanate chloride |
| CN112430295B (en) * | 2019-08-26 | 2022-09-20 | 万华化学集团股份有限公司 | Dechlorinating agent, preparation method thereof and application of dechlorinating agent in reducing chlorine content and chromaticity of isocyanate |
| CN111018176A (en) * | 2019-12-12 | 2020-04-17 | 陕西欧菲德环保科技有限公司 | Demulsifier, preparation method and application thereof |
| CN111732735A (en) * | 2020-06-11 | 2020-10-02 | 长江大学 | Hyperbranched polymer-SiO2Composite demulsifier and preparation method and application thereof |
| CN111732735B (en) * | 2020-06-11 | 2022-08-02 | 长江大学 | Hyperbranched polymer-SiO 2 Composite demulsifier and preparation method and application thereof |
| CN113201105A (en) * | 2021-04-12 | 2021-08-03 | 中海油能源发展股份有限公司 | Interface active type core-shell microsphere for oil extraction and preparation method thereof |
| CN113201105B (en) * | 2021-04-12 | 2022-07-01 | 中海油能源发展股份有限公司 | Interface active type core-shell microsphere for oil extraction and preparation method thereof |
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