CN110041474B - Organic/inorganic hybrid cation reverse demulsifier and preparation method and application thereof - Google Patents
Organic/inorganic hybrid cation reverse demulsifier and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an organic/inorganic hybrid cation reverse demulsifier, and a preparation method and application thereof. The preparation method of the organic/inorganic hybrid cation reverse demulsifier comprises the following steps: 1) adopting silane coupling agent to carry out coupling treatment on nano SiO2Surface hydroxyl modification is carried out to obtain modified nano SiO2Modified nano SiO2The tail end of the surface is connected with a carbon-carbon double bond; 2) modified nano SiO2And carrying out ternary polymerization reaction on acrylamide and dimethyl diallyl ammonium chloride to obtain the compound. The invention uses silane coupling agent containing unsaturated double bond to nano SiO2Modified nano SiO2The demulsifier has certain hydrophobicity, has unsaturated carbon-carbon double bonds at the tail end, can form a net structure of a hydrophobic hard core hydrophilic soft shell by ternary polymerization with AM and DMDAAC, can effectively improve the charge density, realizes effective demulsification on the basis of ensuring low cationic degree, and has low floc strength and high deoiling rate because the demulsifier to be compatible with the reverse demulsifier is nonionic.
Description
Technical Field
The invention relates to an organic/inorganic hybrid cation reverse demulsifier, a preparation method and application thereof, belonging to the field of petrochemical industry.
Background
With the wide application of polymer flooding in tertiary oil recovery technology, the emulsification degree of crude oil water is higher and higher, the demulsification difficulty is higher and higher, and the oil content in the demulsified and dehydrated water is higher and higher on the basis of ensuring the low dosage of the demulsifier, so that the requirement is to provide a medicament which can be compounded with the demulsifier and can effectively reduce the oil content in the demulsified and dehydrated water, namely a reverse demulsifier. According to relevant literature research, the traditional reverse demulsifier mainly uses cations as main materials, and is characterized in that the surfaces of oil drops have negative charges, so that a medicament can be combined with the oil drops through charge neutralization, the oil-water interfacial film tension is further effectively reduced, and finally the demulsification of clear water is realized. It is desirable to provide a low cationicity reverse demulsifier.
Disclosure of Invention
The invention aims to provide an organic/inorganic hybrid cation reverse demulsifier and a preparation method and application thereof, and the invention firstly uses a silane coupling agent (gamma-methacryloxypropyltrimethoxysilane (KH570)) to react with nano SiO of terminal hydroxyl2Modifying to make the tail end have double bond, then making ternary copolymerization with Acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC) to obtain a net structure of hydrophobic hard core and hydrophilic soft shell; the provided organic/inorganic hybrid cation reverse demulsifier has the characteristics of rapid demulsification, high deoiling efficiency and generation of lower-strength oil floc.
The preparation method of the organic/inorganic hybrid cation reverse demulsifier provided by the invention comprises the following steps:
1) adopting silane coupling agent to carry out coupling treatment on nano SiO2Surface hydroxyl modification is carried out to obtain modified nano SiO2The modified nano SiO2The tail end of the surface is connected with a carbon-carbon double bond;
2) the modified nano SiO2And carrying out ternary polymerization reaction on acrylamide and dimethyl diallyl ammonium chloride to obtain the organic/inorganic hybrid cation reverse-phase demulsifier.
In the above preparation method, in step 1), the silane coupling agent may be γ -methacryloxypropyltrimethoxysilane or γ -aminopropyltriethoxysilane;
when the silane coupling agent is gamma-methacryloxypropyltrimethoxysilane, the structural formula of the obtained organic/inorganic hybrid cation reverse-phase demulsifier is shown as a formula I, and a formula II is a corresponding molecular structure schematic diagram:
in the formula I, a is more than or equal to 1; b is more than or equal to 1; c is more than or equal to 1;
r' represents a group of formula III:
in formula II, the blue circle represents the nanosilica, the 8 branches attached to the blue circle represent the silane coupling agent, and the curve attached to the branches represents the polymer.
In the preparation method, in the step 1), the mixed solution of ethanol and water is adopted to prepare the nano SiO2Adjusting the pH value of the solution to 1-6 by adopting acid, and adding the silane coupling agent into the nano SiO2In the solution of (1);
the volume ratio of the water to the ethanol can be 0.5-5: 1, preferably 1 to 3: 1;
the pH value is preferably 3-5;
preparing the nano SiO2Can be dissolved inThe method comprises the following steps: using ultrasound to make the nano SiO2Uniformly dispersing the mixture in the mixed solution of ethanol and water, adjusting the pH value to 1-6 by adopting 2mol/L HCl solution, stirring the mixture in a magnetic stirrer for 1min every 5min within the period of 10-40 min, and finally obtaining uniformly dispersed nano SiO2A solution;
the molar consumption of the silane coupling agent is that of the nano SiO21-30 times, preferably 4-20 times or 10 times of the amount of surface hydroxyl groups;
the nano SiO2The number of surface hydroxyl groups can be determined as follows:
mixing a certain amount (Wg) of nano SiO2Putting the solid powder into a 100mL conical flask, stirring for 24 hours under a sealed condition by adopting 80mL of 0.05mol/L NaOH solution to fully disperse the solid powder in an alkali solution, centrifuging to obtain CmL solution (approximately equal to 80mL), measuring 10mL of separated CmL solution, titrating to be neutral by adopting 0.05mol/L HCl solution, and recording the consumption of the HCl solution as A mL; finally, the remaining solution (C-10) mL was titrated with HCl solution, the consumption of HCl solution was recorded as B mL, and finally according to the formula:
finally calculating to obtain the nano SiO2The content of surface hydroxyl groups.
In the preparation method, in the step 1), the temperature of the surface hydroxyl modification can be 30-100 ℃, preferably 40-80 ℃, and the time can be 0.5-10 hours, preferably 3-8 hours;
after the surface hydroxyl modification is finished, separating and purifying after ethanol dispersion: adding ethanol for dispersion, performing centrifugal separation at the rotating speed of a centrifugal machine of 7000-12000 rmp/min multiplied by 5min, re-dispersing the ethanol, and repeating for 2-6 times.
In the preparation method, in the step 2), the modified nano SiO2The dosage of the acrylamide is 0.1-5% of the total mass of the acrylamide and the dimethyl diallyl ammonium chloride, and specifically can be 0.1-2%;
the mass ratio of the acrylamide to the dimethyl diallyl ammonium chloride can be 0.1-5: 1, specifically, it can be 0.1-2: 1;
the solvent adopted in the ternary polymerization reaction is at least one of water, ethanol, methanol and toluene.
In the preparation method, in the step 2), the temperature of the ternary polymerization reaction is 20-90 ℃ and the time is 0.5-10 h.
In the preparation method, in the step 2), a water-soluble redox initiation system is adopted in the ternary polymerization reaction;
in the water-soluble redox initiation system, the oxidant is at least one of hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate and hydroperoxide, and the reducing agent is an inorganic reducing agent or an organic reducing agent;
the inorganic reducing agent is Fe2+、Cu+、NaHSO3And Na2SO3At least one of (1);
the organic reducing agent is at least one of tetramethylethylenediamine, oxalic acid and alcohol;
sequentially adding the water-soluble redox initiation system into the mixture after oxidation and reduction for 1-6 times;
the dosage of the water-soluble redox initiation system is 0-1% of the total mass of the acrylamide and the dimethyl diallyl ammonium chloride, but is not zero;
the molar ratio of the oxidizing agent to the reducing agent is 1: 1;
the ternary polymerization reaction is carried out under the protection of nitrogen.
And slowly pouring the system after the ternary polymerization reaction into a solvent ethanol, acetone and/or anhydrous ether, precipitating, drying and grinding to finally obtain a crude product of the organic/inorganic hybrid cation reverse-phase demulsifier (PNAD).
The organic/inorganic hybrid cation reverse demulsifier prepared by the method can be used for treating oily sewage, namely carrying out deoiling treatment.
When the organic/inorganic hybrid cation reverse demulsifier is compounded with the demulsifier (dehydration) and the reverse demulsifier (clear water) are sequentially added), the organic/inorganic hybrid cation reverse demulsifier can be used for treating water-in-oil emulsion, and can be used for treating clear water.
The demulsifier may be a nonionic demulsifier conventional in the art, such as a phenolic amine resin polyether demulsifier.
The dosage of the demulsifier is 100mg/L, and the dosage of the organic/inorganic hybrid cation reverse-phase demulsifier is 150-500 mg/L.
The invention uses silane coupling agent containing unsaturated double bond to nano SiO2Modified nano SiO2The demulsifier has certain hydrophobicity, has unsaturated carbon-carbon double bonds at the tail end, can form a net structure of a hydrophobic hard core hydrophilic soft shell by ternary polymerization with AM and DMDAAC, can effectively improve the charge density, realizes effective demulsification on the basis of ensuring low cationic degree, and has low floc strength and high deoiling rate because the demulsifier to be compatible with the reverse demulsifier is nonionic. The preparation method of the reverse demulsifier has the advantages of simple preparation process and low raw material cost, and is very suitable for industrial application.
Drawings
FIG. 1 is a diagram showing the effect of the reverse demulsifier PNAD-1/2/3 when used alone in combination with fresh water.
FIG. 2 is a clear water effect diagram of the combination of the reverse demulsifier PNAD-1/2/3 and the demulsifier A of the invention.
FIG. 3 is a diagram of the dehydration rate of the reverse demulsifier PNAD-1/2/3 compounded with demulsifier A of the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The dehydration rate in the following examples was measured by the color tube method and was equal to the ratio of the amount of water removed after addition of demulsifier a to the total water content of the original emulsion.
Demulsifier a in the following examples is a phenol amine resin polyether demulsifier, and was prepared as follows:
uniformly mixing a certain amount of bisphenol A (bisphenol-based propane) and tetraethylenepentamine with the molar weight 4 times that of the bisphenol A, heating to about 150 ℃ to completely dissolve the bisphenol A, cooling to 50 ℃, dropwise adding formaldehyde solution with the molar weight equal to that of the tetraethylenepentamine, keeping the temperature at 50 ℃, and after dropwise adding, carrying out heat preservation reaction for 2 hours. Adding a certain amount of dimethylbenzene, heating to 100-110 ℃, and carrying out reflux reaction for 2 hours. Slowly heating to carry out water under reflux, and after the water is basically evaporated, evaporating xylene from the material under vacuum condition to obtain the phenol-amine resin initiator.
Adding the initiator and the catalyst KOH into a high-pressure reaction kettle, starting to heat, vacuumizing by using a vacuum pump at normal temperature until the gauge pressure is about-0.1 MPa, purging and replacing by using nitrogen, vacuumizing for 30min, starting to intermittently add PO at 120 +/-5 ℃, and controlling the pressure of the reaction kettle at 0.2-0.4 MPa. After the addition is finished, when the pressure of the reaction kettle falls back, the reaction is continued at the temperature until the pressure is reduced to-0.05 MPa at the beginning, and the reaction is considered to be complete at this moment, so that the lipophilic head is prepared. Putting the lipophilic head and KOH into a reaction kettle, heating to 120 +/-5 ℃ consistent with the step of preparing the lipophilic head, intermittently adding EO, controlling the pressure to be 0.2-0.4 MPa, continuously reacting at the temperature until the pressure is reduced to-0.05 MPa at the beginning when the pressure of the reaction kettle falls after the feeding is finished, and determining that the reaction is complete to prepare the block polyether, wherein the formula is shown as formula 1:
adding the block polyether and xylene (ensuring that the mass concentration of the xylene after the reaction is finished is 50%) into a three-neck flask with mechanical stirring, and heating the three-neck flask to 55 ℃ by using an oil bath kettle. Slowly dripping a quantitative 10% PM-200 (polymethylene polyphenyl polyisocyanate) xylene solution into a three-necked bottle by using a constant-pressure dropping funnel, keeping the temperature constant, and heating to 65 ℃ after finishing dripping to react for 1h to obtain the 50% demulsifier A.
Example 1 preparation of organic/inorganic hybrid cationic reverse demulsifier PNAD-1
(1) Weighing 2g of nano SiO2Stirring in 100ml conical flask with 0.05mol/L NaOH solution 80ml under sealed condition for 24h to disperse it in alkali solutionIn the solution, centrifuging to obtain C mL solution, (≈ 80mL), measuring 10mL from the separated CmL solution, titrating 10mL of C solution to neutrality by using 0.05mol/L HCl, recording the consumption of the HCl solution as A mL, finally titrating the rest solution (C-10) mL by using the HCl solution, recording the consumption of the HCl solution as B mL, and finally obtaining the solution according to the formula:
finally, the surface content of the silicon hydroxyl is calculated to be 5.35 mmol/g;
(2) ultrasonic treatment of 5g of nano-SiO2Uniformly dispersed in 70ml (V) of mixed solvent of ethanol and water(Water/ethanol)2mol/L HCl solution is adopted to adjust the pH value to 4, the time is 30min, the mixture is placed in a magnetic stirrer for stirring for 1min every 5min, and finally the uniformly dispersed nano SiO is obtained270ml of solution containing 5g of nano-SiO2；
(3) Uniformly dispersing the nano SiO obtained in the step (2)2The solution was placed in a 250ml three-necked flask, and a silane coupling agent KH570 was mixed with SiO2Surface hydroxyl number molar ratio of 10: 1, adding 62.69g of the mixture, slowly dropping the mixture into a reaction bottle at a constant speed, and reacting for 4 hours at the temperature of 50 ℃ to obtain the modified nano SiO2A crude product;
(4) the modified nano SiO obtained in the step (3)2Cooling the crude product to room temperature, washing the inner wall of the reaction bottle with 10ml ethanol, pouring into a centrifugal tube, centrifuging at 8000rmp/min × 5min, redispersing with ethanol, repeating for 3 times, and separating to obtain purified modified nanometer SiO2Solution of nano SiO modified therein2The content is 4.5 g;
(5) taking 0.5g of the modified nano SiO obtained in the step (4)2Ultrasonic dispersion in water; weighing 6.94g of monomer AM and 13.79g of DMDAA; uniformly mixing the reaction solution, placing the mixture in an oil bath pan, and reacting for 0.5h at the temperature of 30 ℃; n is a radical of2Protecting, namely sequentially adding an initiator after oxidation and reduction for 3 times;
(6) the polymer is synthesized by adopting a water-soluble redox initiation system, and 1.2498g of initiator is weighed, wherein the oxidant is selected from ammonium persulfate; the reducing agent is organic reducing agent tetramethyl ethylene diamine, and the molar ratio of the organic reducing agent tetramethyl ethylene diamine to the organic reducing agent tetramethyl ethylene diamine is 1: 1;
(7) and (3) slowly pouring 57.16g of the terpolymer PNAD solution obtained in the step (5) into solvent ethanol, precipitating, drying and grinding to finally obtain 38.79g of polymer PNAD-1.
The organic/inorganic hybrid cation reverse demulsifier PNAD-1 prepared in the embodiment is applied to the research of crude oil emulsion in oily sewage and the compounding of demulsifier A, and comprises the following steps:
(1) taking 5ml of oily sewage into a 10ml centrifugal tube, adding 0.075ml, 0.10ml, 0.125ml and 0.15ml of polymer PNAD-1 solution (the adding amount is 150mg/L, 200mg/L, 250mg/L and 300mg/L respectively), oscillating in an oscillator of 3000rmp/min, and then placing in a constant temperature water bath at 70 ℃ for 1 h; the demulsified sewage is subjected to oil extraction by pure hexane through high performance liquid chromatography, the oil content in the water is respectively 9287mg/L, 7245mg/L, 5713mg/L and 2444mg/L by using a portable water oil content instrument of Santa Clara TD-500D, and the oil removal rate respectively reaches 53.57%, 63.78%, 71.44% and 87.78% by calculation.
The effect of using 0.15ml of the polymer PNAD-1 solution in clear water is shown in FIG. 1.
(2) Taking 30ml of oily sewage and 30ml of crude oil emulsion into a 100ml centrifuge tube with a plug, firstly adding 0.6ml of demulsifier A (the adding amount is 100mg/L), then respectively adding 0.9ml, 1.2ml, 1.5m and 1.8ml of polymer PNAD-1 solution (the adding amounts are 150mg/L, 200mg/L, 250mg/L and 300mg/L), oscillating in a shaking table oscillator of 800rmp/min, and then placing in a constant temperature water bath at 70 ℃ for 1 h; the dewatering volume is read according to visual inspection, and the calculated dewatering rate respectively reaches 94%, 81.2%, 85% and 83%; the demulsified sewage is subjected to oil extraction by using pure hexane through high performance liquid chromatography, the oil content in the water is respectively 5879, 3465, 1987 and 2444mg/L by using a portable water oil content instrument of Santa Clara TD-500D, the effect diagram after being cleaned with water is shown in figure 2(a), and the dehydration rate is shown in figure 3 (a).
Example 2 preparation of organic/inorganic hybrid cationic reverse demulsifier PNAD-2
(1) Weighing 2g of nano SiO2In a 100ml coneIn a bottle, 80ml of 0.05mol/L NaOH solution is adopted to be stirred for 24 hours under the sealing condition, so that the NaOH solution is fully dispersed in the alkali solution, the C ml solution is obtained by centrifugation, 10ml of the C solution is titrated to be neutral by adopting 0.05mol/L HCl, the consumption is recorded as A ml, finally, the (C-10) ml solution is titrated by utilizing the HCl solution, the consumption is recorded as B ml, and finally, according to the formula:
finally, the surface content of the silicon hydroxyl is calculated to be 5.25 mmol/g;
(2) ultrasonic treatment of 5g of nano-SiO2Uniformly dispersed in 70ml (V) of mixed solvent of ethanol and water(Water/ethanol)2mol/L HCl solution is adopted to adjust the pH value to 4, the time is 30min, the mixture is placed in a magnetic stirrer for stirring for 1min every 5min, and finally the uniformly dispersed nano SiO is obtained270ml of solution containing 5g of nano-SiO2；
(3) Uniformly dispersing the nano SiO obtained in the step (2)2The solution was placed in a 250ml three-necked flask, and a silane coupling agent KH570 was mixed with SiO2Surface hydroxyl number molar ratio of 10: 1, adding 62.69g of the mixture, slowly dropping the mixture into a reaction bottle at a constant speed, and reacting for 4 hours at the temperature of 50 ℃ to obtain the modified nano SiO2A crude product;
(4) the modified nano SiO obtained in the step (3)2Cooling the crude product to room temperature, washing the inner wall of the reaction bottle with 10ml ethanol, pouring into a centrifugal tube, centrifuging at 8000rmp/min × 5min, redispersing with ethanol, repeating for 3 times, and separating to obtain purified modified nanometer SiO2Solution of nano SiO modified therein2The content is 4.5 g;
(5) taking 0.5g of the modified nano SiO obtained in the step (4)2Ultrasonic dispersion in water; weighing 5.21g of monomer AM and 15.62g of DMDAAC; uniformly mixing the reaction solution, placing the mixture in an oil bath pan, and reacting for 0.5h at the temperature of 30 ℃; n is a radical of2Protecting, namely sequentially adding an initiator after oxidation and reduction for 3 times;
(6) the polymer is synthesized by adopting a water-soluble redox initiation system, and 1.2498g of initiator is weighed, wherein the oxidant is selected from ammonium persulfate; the reducing agent is organic reducing agent tetramethyl ethylene diamine;
(7) and (3) slowly pouring 57.16g of the terpolymer PNAD solution obtained in the step (5) into solvent ethanol, precipitating, drying and grinding to obtain 34.30g of polymer PNAD-2.
The organic/inorganic hybrid cation reverse demulsifier PNAD-2 is applied to the research of crude oil emulsion in oily sewage and the compounding of demulsifier A, and comprises the following steps:
(1) taking 5ml of oily sewage into a 10ml centrifugal tube, adding 0.075ml, 0.10ml, 0.125ml and 0.15ml of polymer PNAD-2 solution (the adding amount is 150mg/L, 200mg/L, 250mg/L and 300mg/L respectively), oscillating in an oscillator of 3000rmp/min, and then placing in a constant temperature water bath at 70 ℃ for 1 h; the demulsified sewage is subjected to oil extraction by pure hexane through high performance liquid chromatography, the oil content in the water is respectively 13257mg/L, 8029mg/L, 4394mg/L and 2610mg/L by an oil content instrument in portable water of America Terna TD-500D, and the deoiling rates respectively reach 33.75%, 59.86%, 78.03% and 86.95% through calculation.
The effect of using 0.15ml of the polymer PNAD-2 solution in clear water is shown in FIG. 1.
(2) Taking 30ml of oily sewage and 30ml of crude oil emulsion into a 100ml centrifuge tube with a plug, firstly adding 0.6ml of demulsifier A (the adding amount is 100mg/L), then respectively adding 0.9ml, 1.2ml, 1.5m and 1.8ml of polymer PNAD-2 solution (the adding amounts are 150mg/L, 200mg/L, 250mg/L and 300mg/L), polymer PNAD-2 solution and 0.6ml of demulsifier A, oscillating in a shaker oscillator of 800rmp/min, and then placing in a constant temperature water bath at 70 ℃ for 1 h; reading the dewatering volume according to visual inspection, and calculating the dewatering rate to reach 85%, 96%, 92% and 85% respectively; the demulsified sewage is subjected to oil extraction by using pure hexane through high performance liquid chromatography, the oil content in the water is respectively 6215, 3783, 1876 and 1444mg/L by using a portable water oil content instrument of Terna TD-500D, the effect diagram after being cleaned with water is shown in figure 2(b), and the dehydration rate is shown in figure 3 (b).
Example 3 preparation of organic/inorganic hybrid cationic reverse demulsifier PNAD-3
(1) Weighing 2g of nanoSiO2Stirring 80ml of 0.05mol/L NaOH solution in a 100ml conical flask for 24 hours under a sealed condition to fully disperse the NaOH solution in an alkali solution, centrifuging to obtain C ml solution, titrating 10ml of C solution to be neutral by using 0.05mol/L HCl, consuming A ml of C solution, finally titrating (C-10) ml solution by using HCl solution, consuming B ml of C solution, and finally calculating according to the formula:
finally, the surface content of the silicon hydroxyl is calculated to be 5.35 mmol/g;
(2) ultrasonic treatment of 5g of nano-SiO2Uniformly dispersed in 70ml (V) of mixed solvent of ethanol and water(Water/ethanol)2mol/L HCl solution is adopted to adjust the pH value to 4, the time is 30min, the mixture is placed in a magnetic stirrer for stirring for 1min every 5min, and finally the uniformly dispersed nano SiO is obtained270ml of solution containing 5g of nano-SiO2；
(3) Uniformly dispersing the nano SiO obtained in the step (2)2The solution was placed in a 250ml three-necked flask, and a silane coupling agent KH570 was mixed with SiO2Surface hydroxyl number molar ratio of 10: 1, adding 62.69g of the mixture, slowly dropping the mixture into a reaction bottle at a constant speed, and reacting for 4 hours at the temperature of 50 ℃ to obtain the modified nano SiO2A crude product;
(4) the modified nano SiO obtained in the step (3)2Cooling the crude product to room temperature, washing the inner wall of the reaction bottle with 10ml ethanol, pouring into a centrifugal tube, centrifuging at 8000rmp/min × 5min, redispersing with ethanol, repeating for 3 times, and separating to obtain purified modified nanometer SiO2Solution of nano SiO modified therein2The content is 4.5 g;
(5) taking 0.5g of the modified nano SiO obtained in the step (4)2Ultrasonic dispersion in water; weighing 3.78g of monomer AM and 17.04g of DMDAAC; uniformly mixing the reaction solution, placing the mixture in an oil bath pan, and reacting for 0.5h at the temperature of 30 ℃; n is a radical of2Protecting, namely sequentially adding an initiator after oxidation and reduction for 3 times;
(6) the polymer is synthesized by adopting a water-soluble redox initiation system, and 1.2498g of initiator is weighed, wherein the oxidant is selected from ammonium persulfate; the reducing agent is organic reducing agent tetramethyl ethylene diamine;
(7) and (3) slowly pouring 57.16g of the terpolymer PNAD solution obtained in the step (5) into solvent ethanol, precipitating, drying and grinding to finally obtain 38.79g of polymer PNAD-3.
The organic/inorganic hybrid cation reverse demulsifier PNAD-3 is applied to the research of crude oil emulsion in oily sewage and the compounding of demulsifier A, and comprises the following steps:
(1) taking 5ml of oily sewage into a 10ml centrifugal tube, adding 0.075ml, 0.10ml, 0.125ml and 0.15ml of polymer PNAD-3 solution (the adding amount is 150mg/L, 200mg/L, 250mg/L and 300mg/L respectively), oscillating in an oscillator of 3000rmp/min, and then placing in a constant temperature water bath at 70 ℃ for 1 h; the demulsified sewage is subjected to oil extraction by pure hexane through high performance liquid chromatography, the oil content in the water is respectively 13473mg/L, 4733mg/L, 954.1mg/L and 1983mg/L by using a portable water oil content instrument of Santa Claus TD-500D, and the oil removal rate respectively reaches 32.64%, 76.34%, 95.23% and 90.10% by calculation.
The effect of using 0.15ml of the polymer PNAD-1 solution in clear water is shown in FIG. 1.
(2) Taking 30ml of oily sewage and 30ml of crude oil emulsion into a 100ml centrifuge tube with a plug, firstly adding 0.6ml of demulsifier A (the adding amount is 100mg/L), then respectively adding 0.9ml, 1.2ml, 1.5m and 1.8ml of polymer PNAD-1 solution (the adding amounts are 150mg/L, 200mg/L, 250mg/L and 300mg/L), oscillating in a shaking table oscillator of 800rmp/min, and then placing in a constant temperature water bath at 70 ℃ for 1 h; the dewatering volume is read according to visual inspection, and the calculated dewatering rate respectively reaches 93.5%, 81.2%, 85% and 81.2%; the demulsified sewage is subjected to oil extraction by pure hexane through high performance liquid chromatography, the oil content in the water is measured by a portable water oil content instrument of Santa Clara TD-500D, the oil content is respectively 5119mg/L, 1827mg/L, 1688mg/L and 1766mg/L, the effect diagram after being cleaned with water is shown in figure 2(c), and the dehydration rate is shown in figure 3 (c).
In conclusion, the deoiling rate of the reverse demulsifier PNAD-1/2/3 can reach more than 80% (300mg/L) when being used alone; the dehydration rate of the crude oil emulsion can reach more than 80 percent after being compounded with the demulsifier, and the oil content in the demulsified and dehydrated water can be as low as about 1 per thousand; can meet the demulsification requirement of the offshore platform.
Claims (5)
1. A preparation method of an organic/inorganic hybrid cation reverse demulsifier comprises the following steps:
1) adopting silane coupling agent to carry out coupling treatment on nano SiO2Surface hydroxyl modification is carried out to obtain modified nano SiO2The modified nano SiO2The tail end of the surface is connected with a carbon-carbon double bond;
the silane coupling agent is gamma-methacryloxypropyltrimethoxysilane;
the temperature of the surface hydroxyl modification is 30-100 ℃, and the time is 0.5-10 h;
after the surface hydroxyl modification is finished, separating and purifying after ethanol dispersion;
2) the modified nano SiO2Carrying out ternary polymerization reaction on acrylamide and dimethyl diallyl ammonium chloride to obtain the organic/inorganic hybrid cation reverse-phase demulsifier;
the modified nano SiO2The dosage of the acrylamide is 0.1-5% of the total mass of the acrylamide and the dimethyl diallyl ammonium chloride;
the mass ratio of the acrylamide to the dimethyl diallyl ammonium chloride is 0.1-5: 1;
the solvent adopted by the ternary polymerization reaction is at least one of water, ethanol, methanol and toluene;
the temperature of the ternary polymerization reaction is 20-90 ℃, and the time is 0.5-10 h;
the ternary polymerization reaction adopts a water-soluble redox initiation system;
in the water-soluble redox initiation system, the oxidant is at least one of hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate, and the reducing agent is an inorganic reducing agent or an organic reducing agent;
the inorganic reducing agent is Fe2+、Cu+、NaHSO3And Na2SO3At least one of (1);
the organic reducing agent is at least one of tetramethylethylenediamine, oxalic acid and alcohol;
sequentially adding the water-soluble redox initiation system into the mixture after oxidation and reduction for 1-6 times;
the dosage of the water-soluble redox initiation system is 0-1% of the total mass of the acrylamide and the dimethyl diallyl ammonium chloride, but is not zero;
the molar ratio of the oxidizing agent to the reducing agent is 1: 1.
2. the method of claim 1, wherein: in the step 1), the mixed solution of ethanol and water is adopted to prepare the nano SiO2Adjusting the pH value of the solution to 1-6 by adopting acid, and adding the silane coupling agent into the nano SiO2In the solution of (1);
the molar consumption of the silane coupling agent is that of the nano SiO21-30 times of surface hydroxyl quantity.
3. An organic/inorganic hybrid cation reverse demulsifier prepared by the method of claim or 2.
4. Use of the organic/inorganic hybrid cation reverse demulsifier of claim 3 in the treatment of oily wastewater.
5. Use of the organic/inorganic hybrid cationic reverse demulsifier of claim 3 for treating water-in-oil emulsions;
the organic/inorganic hybrid cation reverse demulsifier and the demulsifier are compounded for use.
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