CN116425994A - Demulsifier for hydrocarbon sewage and preparation method thereof - Google Patents
Demulsifier for hydrocarbon sewage and preparation method thereof Download PDFInfo
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- CN116425994A CN116425994A CN202310684234.1A CN202310684234A CN116425994A CN 116425994 A CN116425994 A CN 116425994A CN 202310684234 A CN202310684234 A CN 202310684234A CN 116425994 A CN116425994 A CN 116425994A
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- demulsifier
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- deionized water
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- acrylic acid
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 22
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 22
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 21
- 239000010865 sewage Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003607 modifier Substances 0.000 claims abstract description 24
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 24
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims abstract description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- 238000001914 filtration Methods 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 25
- 239000000706 filtrate Substances 0.000 claims description 25
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 18
- -1 polysiloxane Polymers 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 17
- 229920001296 polysiloxane Polymers 0.000 claims description 17
- BCSWGORLHAAHNS-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctyl-bis(trifluoromethoxy)-(trifluoromethyl)silane Chemical compound FC(F)(F)O[Si](OC(F)(F)F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BCSWGORLHAAHNS-UHFFFAOYSA-N 0.000 claims description 16
- PELGKMTVNFFDDL-UHFFFAOYSA-N dodecyl-dimethoxy-methylsilane Chemical compound CCCCCCCCCCCC[Si](C)(OC)OC PELGKMTVNFFDDL-UHFFFAOYSA-N 0.000 claims description 16
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 125000003277 amino group Chemical group 0.000 claims description 14
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 5
- 239000010779 crude oil Substances 0.000 abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000839 emulsion Substances 0.000 abstract description 5
- 229920000570 polyether Polymers 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract description 2
- 239000000693 micelle Substances 0.000 abstract description 2
- 229920000058 polyacrylate Polymers 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000000605 extraction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
- B01D17/047—Breaking emulsions with separation aids
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a demulsifier for hydrocarbon sewage and a preparation method thereof, and relates to the technical field of demulsifiers. The modified carrier is dispersed in DMF, acrylic acid is added, under the action of p-toluenesulfonic acid, the acrylic acid is esterified with hydroxyl on the surface to prepare a functional carrier, the functional carrier, a modifier and methacryloyloxyethyl trimethyl ammonium chloride are polymerized to prepare the demulsifier, the surface of the demulsifier contains hyperbranched polyacrylate structures, the hyperbranched structures contain organic silicon chain segments, long-chain fluoroalkyl and long-chain alkyl, so that the demulsifier has the effect of reducing surface tension, the surface tension of an oil-water interfacial film can be further reduced by matching with polyether chain segments on the surface, the hyperbranched structure on the surface is unfavorable for forming micelles, the demulsifier can be easily adsorbed on the oil-water interfacial film of crude oil emulsion, the wettability of the oil-water interfacial film is enhanced, the stability of the crude oil emulsion is destroyed, and the demulsifier can form a weak interfacial film on the surface of the oil-water interfacial film.
Description
Technical Field
The invention relates to the technical field of demulsifier preparation, in particular to a demulsifier for hydrocarbon sewage and a preparation method thereof.
Background
Petroleum is a flammable viscous liquid produced from underground, is brown, brown or black in color, has a density less than that of water, and is a very complex mixture of components. The composition and performance of the petroleum exploitation are greatly influenced by different times and different geological layers. The main components of petroleum are various hydrocarbons (alkane, naphthene and aromatic hydrocarbon), and a small amount of non-hydrocarbon components, and along with the rapid development of petroleum exploitation and petroleum processing industry, various oil extraction processes and yield increasing measures are continuously increased to stabilize the production of crude oil, so that the composition of the thick oil produced liquid becomes more complex. So that the efficient and rapid demulsification of the thick oil and the ultra-thick oil has become a key technology for influencing the oil extraction cost, the crude oil quality, the yield and controlling the environmental pollution of the oil field. Therefore, research, development, production and application of novel efficient crude oil demulsifiers, in particular thickened oil and super thickened oil demulsifiers, have become an increasingly popular topic in oilfield chemistry, and the existing demulsifiers mainly comprise nonionic polyoxypropylene-polyoxyethylene block polymers: alcohol polyether demulsifier, polyethylene polyamine block polyether demulsifier, phenolic resin series demulsifier and silicon-containing demulsifier using alcohol as initiator, but the demulsifier at the present stage has low demulsification efficiency, so that the oil extraction cost is still affected.
Disclosure of Invention
The invention aims to provide a demulsifier for hydrocarbon sewage and a preparation method thereof, which solve the problems that the demulsifier at the present stage has an unsatisfactory demulsification effect and cannot be recovered.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the demulsifier for the hydrocarbon sewage specifically comprises the following steps:
step S1: dispersing the modified carrier in toluene, adding acrylic acid and p-toluenesulfonic acid, reacting for 3-5h under the conditions of the rotating speed of 300-500r/min and the temperature of 110-120 ℃, and filtering to remove filtrate to obtain a functionalized carrier;
step S2: uniformly mixing a functional carrier, a modifier, methacryloxyethyl trimethyl ammonium chloride and toluene, introducing nitrogen for protection, adding potassium persulfate under the condition of the rotating speed of 120-150r/min and the temperature of 75-80 ℃ for reacting for 5-7h, and filtering to remove filtrate to obtain the demulsifier.
In step S1, the modified carrier contains amino, the molar ratio of the amino to the acrylic acid is 1:1, and the dosage of the p-toluenesulfonic acid is 5% of the mass of the acrylic acid.
In step S2, the mass ratio of the functionalized carrier to the modifier to the methacryloyloxyethyl trimethyl ammonium chloride is 1:52:6, and the dosage of the potassium persulfate is 1-1.5% of the mass of the methacryloyloxyethyl trimethyl ammonium chloride.
Further, the modifier is prepared by the following steps:
step A1: mixing perfluorooctyl methyl dimethoxy silane, dodecyl methyl dimethoxy silane and deionized water, stirring for 10-15min at the rotation speed of 200-300r/min and the temperature of 60-70 ℃, adding concentrated sulfuric acid and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, reacting for 4-6h, and regulating pH to be neutral to obtain diamine-terminated polysiloxane;
step A2: dissolving methyl acrylate in methanol, adding sodium hydroxide, introducing nitrogen for protection, stirring and adding ethylenediamine under the conditions of the rotating speed of 90-120r/min and the temperature of 0-3 ℃, heating to 20-25 ℃, reacting for 20-25h to obtain an intermediate 1, adding diamine-terminated polysiloxane, continuing to react for 20-25h to obtain hyperbranched amine, uniformly mixing the hyperbranched amine, acrylic acid, DCC and toluene, and reacting for 3-5h under the conditions of the rotating speed of 200-300r/min and the temperature of 30-40 ℃ to obtain the modifier.
Further, the dosage ratio of perfluorooctyl methyl dimethoxy silane, dodecyl methyl dimethoxy silane, deionized water and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane in the step A1 is 5mmol, 2mmol, 10mL, 5mmol, and concentrated sulfuric acid is 8-10% of the sum of the weights of perfluorooctyl methyl dimethoxy silane, dodecyl methyl dimethoxy silane and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane.
Further, the molar ratio of methyl acrylate to ethylenediamine in the step A2 is 1:4, the molar ratio of the intermediate 1 to the diamine-terminated polysiloxane is n (3n+1), n is a natural number greater than 0, the hyperbranched amine contains amino groups, and the molar ratio of the amino groups, the acrylic acid and DCC is 1:1:1.2.
Further, the modified carrier is prepared by the following steps:
step B1: dispersing ferroferric oxide in deionized water, adding isopropanol, stirring and adding ethyl orthosilicate under the conditions of the rotating speed of 120-150r/min, the temperature of 60-70 ℃ and the pH value of 11-12, reacting for 10-15 hours, filtering to remove filtrate, dispersing a substrate in ethanol, adding deionized water, carrying out reflux treatment for 2-3 hours under the conditions of the temperature of 90-95 ℃, filtering and drying to obtain a pretreatment carrier;
step B2: dispersing the pretreated carrier in ethanol, adding deionized water, mixing uniformly, stirring at the rotation speed of 200-300r/min and the temperature of 20-25 ℃, adding KH550, reacting for 10-15h, filtering to remove filtrate, dispersing the substrate in DMF, adding potassium hydroxide, reacting for 6-8h at the temperature of 125-135 ℃ and the pressure of-0.1 MPa, adding propylene oxide, reacting for 4-5h at the temperature of 115-125 ℃ continuously, and filtering to remove filtrate to obtain the modified carrier.
Further, the dosage ratio of the ferroferric oxide, deionized water, isopropyl alcohol and ethyl orthosilicate in the step B1 is 1.25g:50mL:100mL:2mL, and the dosage ratio of the substrate, ethanol and deionized water is 80mg:14mL:1mL.
Further, the ratio of the pretreated carrier, ethanol, deionized water and KH550 in the step B2 is 100mg:50mL:5mL:0.2mL, the mass ratio of the substrate, propylene oxide and ethylene oxide is 1:69:34.5, and the amount of potassium hydroxide is 15-20% of the sum of the mass of propylene oxide and ethylene oxide.
The invention has the beneficial effects that: according to the demulsifier for hydrocarbon sewage, the modified carrier is dispersed in DMF, acrylic acid is added, and under the action of p-toluenesulfonic acid, the acrylic acid is esterified with hydroxyl on the surface to prepare the functionalized carrier; polymerizing the functional carrier, the modifier and the methacryloyloxyethyl trimethyl ammonium chloride to prepare a demulsifier; the modifier is prepared by taking perfluorooctyl methyldimethoxy silane and dodecyl methyldimethoxy silane as raw materials, hydrolyzing, polymerizing with 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane to form diamine-terminated polysiloxane, reacting methyl acrylate with ethylenediamine to enable double bonds on the methyl acrylate to be grafted with amino groups on the ethylenediamine, adding the diamine-terminated polysiloxane to enable the methyl acrylate to react with the amino groups to prepare hyperbranched amine, dehydrating and condensing the hyperbranched amine with acrylic acid and carboxyl groups on the acrylic acid under the action of DCC to prepare the modifier; the modified carrier is prepared by taking ferroferric oxide as a raw material, adding tetraethoxysilane for hydrolytic polymerization, forming nano silicon dioxide on the surface of the ferroferric oxide, refluxing under the conditions of ethanol and deionized water to increase the surface hydroxyl, preparing a pretreated carrier, carrying out surface treatment on the pretreated carrier by KH550 to graft a large amount of active amino on the surface of the pretreated carrier, adding propylene oxide, enabling part of propylene oxide to react with the surface active amino, and polymerizing with the rest of propylene oxide and ethylene oxide to form polyether on the surface. The demulsifier is a magnetic demulsifier, the surface of the demulsifier contains a hyperbranched polyacrylate structure, the hyperbranched structure contains an organosilicon chain segment, long-chain fluoroalkyl and long-chain alkyl, so that the demulsifier has the effect of reducing surface tension, the surface tension of an oil-water interfacial film can be further reduced by matching with a polyether chain segment on the surface, the hyperbranched structure on the surface is unfavorable for association to form micelles, the demulsifier can be easily adsorbed on the oil-water interfacial film of the crude oil emulsion, the wettability of the oil-water interfacial film is further enhanced, the stability of the crude oil emulsion is further damaged, the demulsifier can form a weak interfacial film on the surface of the oil-water interface, and under the action of an external magnetic field, the liquid drops of the crude oil emulsion are rapidly reduced, so that the film structure is broken, and then the demulsification effect is achieved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the demulsifier for the hydrocarbon sewage specifically comprises the following steps:
step S1: dispersing the modified carrier in toluene, adding acrylic acid and p-toluenesulfonic acid, reacting for 3 hours under the conditions of the rotating speed of 300r/min and the temperature of 110 ℃, and filtering to remove filtrate to obtain a functionalized carrier;
step S2: uniformly mixing a functionalized carrier, a modifier, methacryloxyethyl trimethyl ammonium chloride and toluene, introducing nitrogen for protection, adding potassium persulfate under the condition of the rotating speed of 120r/min and the temperature of 75 ℃ for reacting for 5 hours, and filtering to remove filtrate to obtain the demulsifier.
The molar ratio of the amino group on the modified carrier to the acrylic acid in the step S1 is 1:1, and the dosage of the p-toluenesulfonic acid is 5% of the mass of the acrylic acid.
The mass ratio of the functionalized carrier to the modifier to the methacryloyloxyethyl trimethyl ammonium chloride in the step S2 is 1:52:6, and the dosage of the potassium persulfate is 1% of the mass of the methacryloyloxyethyl trimethyl ammonium chloride.
The modifier is prepared by the following steps:
step A1: mixing perfluorooctyl methyl dimethoxy silane, dodecyl methyl dimethoxy silane and deionized water, stirring for 10min at the rotation speed of 200r/min and the temperature of 60 ℃, adding concentrated sulfuric acid and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, reacting for 4h, and regulating the pH value to be neutral to obtain diamine-terminated polysiloxane;
step A2: dissolving methyl acrylate in methanol, adding sodium hydroxide, introducing nitrogen for protection, stirring and adding ethylenediamine under the condition of the rotating speed of 90r/min and the temperature of 0 ℃, heating to 20 ℃, reacting for 20 hours to obtain an intermediate 1, adding diamine-terminated polysiloxane, continuing to react for 20 hours to obtain hyperbranched amine, uniformly mixing the hyperbranched amine, acrylic acid, DCC and toluene, and reacting for 3 hours under the condition of the rotating speed of 200r/min and the temperature of 30 ℃ to obtain the modifier.
The dosage ratio of perfluorooctyl methyl dimethoxy silane, dodecyl methyl dimethoxy silane, deionized water and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane in the step A1 is 5mmol, 2mmol, 10mL, 5mmol, and concentrated sulfuric acid is 8% of the sum of the perfluorooctyl methyl dimethoxy silane, dodecyl methyl dimethoxy silane and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane.
The molar ratio of methyl acrylate to ethylenediamine in the step A2 is 1:4, the molar ratio of the intermediate 1 to the diamine-terminated polysiloxane is 1:4, and the molar ratio of amino groups on the hyperbranched amine, acrylic acid and DCC is 1:1:1.2.
The modified carrier is prepared by the following steps:
step B1: dispersing ferroferric oxide in deionized water, adding isopropanol, stirring and adding tetraethoxysilane under the conditions of the rotating speed of 120r/min, the temperature of 60 ℃ and the pH value of 11, reacting for 10 hours, filtering to remove filtrate, dispersing a substrate in ethanol, adding deionized water, carrying out reflux treatment for 2 hours under the condition of the temperature of 90 ℃, filtering and drying to obtain a pretreated carrier;
step B2: dispersing the pretreated carrier in ethanol, adding deionized water, mixing uniformly, stirring at a rotation speed of 200r/min and a temperature of 20 ℃, adding KH550, reacting for 10 hours, filtering to remove filtrate, dispersing the substrate in DMF, adding potassium hydroxide, adding propylene oxide at a temperature of 125 ℃ and a pressure of-0.1 MPa, reacting for 6 hours, adding ethylene oxide, reacting for 4 hours at a temperature of 115 ℃, filtering to remove filtrate, and obtaining the modified carrier.
The dosage ratio of the ferroferric oxide, deionized water, isopropyl alcohol and tetraethoxysilane in the step B1 is 1.25g:50mL:100mL:2mL, and the dosage ratio of the substrate, ethanol and deionized water is 80mg:14mL:1mL.
The ratio of the pretreatment carrier, ethanol, deionized water and KH550 in the step B2 is 100mg:50mL:5mL:0.2mL, the mass ratio of the substrate, propylene oxide and ethylene oxide is 1:69:34.5, and the KOH is 15% of the sum of the mass of propylene oxide and ethylene oxide.
Example 2
The preparation method of the demulsifier for the hydrocarbon sewage specifically comprises the following steps:
step S1: dispersing the modified carrier in toluene, adding acrylic acid and p-toluenesulfonic acid, reacting for 4 hours under the conditions of the rotating speed of 300r/min and the temperature of 115 ℃, and filtering to remove filtrate to obtain a functionalized carrier;
step S2: uniformly mixing a functionalized carrier, a modifier, methacryloxyethyl trimethyl ammonium chloride and toluene, introducing nitrogen for protection, adding potassium persulfate under the condition of the rotating speed of 150r/min and the temperature of 78 ℃ for reaction for 6 hours, and filtering to remove filtrate to obtain the demulsifier.
The molar ratio of the amino group on the modified carrier to the acrylic acid in the step S1 is 1:1, and the dosage of the p-toluenesulfonic acid is 5% of the mass of the acrylic acid.
The mass ratio of the functionalized carrier to the modifier to the methacryloyloxyethyl trimethyl ammonium chloride in the step S2 is 1:52:6, and the dosage of the potassium persulfate is 1.2 percent of the mass of the methacryloyloxyethyl trimethyl ammonium chloride.
The modifier is prepared by the following steps:
step A1: mixing perfluorooctyl methyl dimethoxy silane, dodecyl methyl dimethoxy silane and deionized water, stirring for 13min at the rotation speed of 200r/min and the temperature of 65 ℃, adding concentrated sulfuric acid and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, reacting for 5h, and regulating the pH value to be neutral to obtain diamine-terminated polysiloxane;
step A2: dissolving methyl acrylate in methanol, adding sodium hydroxide, introducing nitrogen for protection, stirring and adding ethylenediamine under the conditions of the rotating speed of 120r/min and the temperature of 2 ℃, heating to 23 ℃, reacting for 23 hours to obtain an intermediate 1, adding diamine-terminated polysiloxane, continuing to react for 25 hours to obtain hyperbranched amine, uniformly mixing the hyperbranched amine, acrylic acid, DCC and toluene, and reacting for 4 hours under the conditions of the rotating speed of 200r/min and the temperature of 35 ℃ to obtain the modifier.
The dosage ratio of perfluorooctyl methyl dimethoxy silane, dodecyl methyl dimethoxy silane, deionized water and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane in the step A1 is 5mmol, 2mmol, 10mL, 5mmol, and concentrated sulfuric acid is 9% of the sum of the perfluorooctyl methyl dimethoxy silane, dodecyl methyl dimethoxy silane and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane.
The molar ratio of methyl acrylate to ethylenediamine in the step A2 is 1:4, the molar ratio of the intermediate 1 to the diamine-terminated polysiloxane is 2:7, and the molar ratio of amino groups on the hyperbranched amine, acrylic acid and DCC is 1:1:1.2.
The modified carrier is prepared by the following steps:
step B1: dispersing ferroferric oxide in deionized water, adding isopropanol, stirring and adding tetraethoxysilane under the conditions of the rotating speed of 150r/min, the temperature of 65 ℃ and the pH value of 11, reacting for 13 hours, filtering to remove filtrate, dispersing a substrate in ethanol, adding deionized water, carrying out reflux treatment for 2.5 hours under the condition of the temperature of 93 ℃, filtering and drying to obtain a pretreated carrier;
step B2: dispersing the pretreated carrier in ethanol, adding deionized water, mixing uniformly, stirring at a rotation speed of 200r/min and a temperature of 23 ℃, adding KH550, reacting for 13h, filtering to remove filtrate, dispersing the substrate in DMF, adding potassium hydroxide, adding propylene oxide at a temperature of 130 ℃ and a pressure of-0.1 MPa, reacting for 7h, adding ethylene oxide, reacting for 4.5h at a temperature of 120 ℃, filtering to remove filtrate, and obtaining the modified carrier.
The dosage ratio of the ferroferric oxide, deionized water, isopropyl alcohol and tetraethoxysilane in the step B1 is 1.25g:50mL:100mL:2mL, and the dosage ratio of the substrate, ethanol and deionized water is 80mg:14mL:1mL.
The ratio of the pretreatment carrier, ethanol, deionized water and KH550 in the step B2 is 100mg:50mL:5mL:0.2mL, the mass ratio of the substrate, propylene oxide and ethylene oxide is 1:69:34.5, and the KOH is 18% of the sum of the mass of propylene oxide and ethylene oxide.
Example 3
The preparation method of the demulsifier for the hydrocarbon sewage specifically comprises the following steps:
step S1: dispersing the modified carrier in toluene, adding acrylic acid and p-toluenesulfonic acid, reacting for 5 hours under the conditions of 500r/min rotating speed and 120 ℃, and filtering to remove filtrate to obtain a functionalized carrier;
step S2: uniformly mixing a functional carrier, a modifier, methacryloxyethyl trimethyl ammonium chloride and toluene, introducing nitrogen for protection, adding potassium persulfate under the condition of the rotating speed of 150r/min and the temperature of 80 ℃ for reaction for 7 hours, and filtering to remove filtrate to obtain the demulsifier.
The molar ratio of the amino group on the modified carrier to the acrylic acid in the step S1 is 1:1, and the dosage of the p-toluenesulfonic acid is 5% of the mass of the acrylic acid.
The mass ratio of the functionalized carrier to the modifier to the methacryloyloxyethyl trimethyl ammonium chloride in the step S2 is 1:52:6, and the dosage of the potassium persulfate is 1.5% of the mass of the methacryloyloxyethyl trimethyl ammonium chloride.
The modifier is prepared by the following steps:
step A1: mixing perfluorooctyl methyl dimethoxy silane, dodecyl methyl dimethoxy silane and deionized water, stirring for 15min at the rotation speed of 300r/min and the temperature of 70 ℃, adding concentrated sulfuric acid and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, reacting for 6h, and regulating the pH value to be neutral to obtain diamine-terminated polysiloxane;
step A2: dissolving methyl acrylate in methanol, adding sodium hydroxide, introducing nitrogen for protection, stirring and adding ethylenediamine under the conditions of the rotating speed of 120r/min and the temperature of 3 ℃, heating to 25 ℃, reacting for 25 hours to obtain an intermediate 1, adding diamine-terminated polysiloxane, continuing to react for 25 hours to obtain hyperbranched amine, uniformly mixing the hyperbranched amine, acrylic acid, DCC and toluene, and reacting for 5 hours under the conditions of the rotating speed of 300r/min and the temperature of 40 ℃ to obtain the modifier.
The dosage ratio of perfluorooctyl methyl dimethoxy silane, dodecyl methyl dimethoxy silane, deionized water and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane in the step A1 is 5mmol, 2mmol, 10mL, 5mmol, and concentrated sulfuric acid is 10% of the sum of the perfluorooctyl methyl dimethoxy silane, dodecyl methyl dimethoxy silane and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane.
The molar ratio of methyl acrylate to ethylenediamine in the step A2 is 1:4, the molar ratio of the intermediate 1 to the diamine-terminated polysiloxane is 3:10, and the molar ratio of amino groups on the hyperbranched amine, acrylic acid and DCC is 1:1:1.2.
The modified carrier is prepared by the following steps:
step B1: dispersing ferroferric oxide in deionized water, adding isopropanol, stirring and adding tetraethoxysilane under the conditions of the rotating speed of 150r/min, the temperature of 70 ℃ and the pH value of 12, reacting for 15 hours, filtering to remove filtrate, dispersing a substrate in ethanol, adding deionized water, carrying out reflux treatment for 3 hours under the condition of the temperature of 95 ℃, filtering and drying to obtain a pretreated carrier;
step B2: dispersing the pretreated carrier in ethanol, adding deionized water, mixing uniformly, stirring at a rotation speed of 300r/min and a temperature of 25 ℃, adding KH550, reacting for 15 hours, filtering to remove filtrate, dispersing the substrate in DMF, adding potassium hydroxide, adding propylene oxide at a temperature of 135 ℃ and a pressure of-0.1 MPa, reacting for 8 hours, adding ethylene oxide, reacting for 5 hours at a temperature of 125 ℃, filtering to remove filtrate, and obtaining the modified carrier.
The dosage ratio of the ferroferric oxide, deionized water, isopropyl alcohol and tetraethoxysilane in the step B1 is 1.25g:50mL:100mL:2mL, and the dosage ratio of the substrate, ethanol and deionized water is 80mg:14mL:1mL.
The ratio of the pretreatment carrier, ethanol, deionized water and KH550 in the step B2 is 100mg:50mL:5mL:0.2mL, the mass ratio of the substrate, propylene oxide and ethylene oxide is 1:69:34.5, and the KOH is 20% of the sum of the mass of propylene oxide and ethylene oxide.
Comparative example 1
This comparative example uses nanosilica instead of pretreated support, as compared to example 1, the rest of the procedure being the same.
Comparative example 2
In this comparative example, the modified support was replaced with the pretreated support, and the rest of the procedure was the same as in example 1.
The demulsifiers prepared in examples 1-3 and comparative examples 1-2 were mixed uniformly and then allowed to stand at 85℃for 3 hours, and the dehydration rate, the oil-water interface condition and the color of the dehydrated water were recorded, with 40mL of acid-containing crude oil, an acid value of 3.51mg/g, a water content of 0.8% by weight and an demulsifier addition amount of 200mg/L, in accordance with SY/T5281-2000 standards.
The table shows that the invention has good demulsification effect.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (10)
1. The preparation method of the demulsifier for the hydrocarbon sewage is characterized by comprising the following steps of:
step S1: dispersing the modified carrier in toluene, adding acrylic acid and p-toluenesulfonic acid, reacting, and filtering to remove filtrate to obtain a functionalized carrier;
step S2: and uniformly mixing the functionalized carrier, the modifier, the methacryloxyethyl trimethyl ammonium chloride and toluene, introducing nitrogen for protection, adding potassium persulfate, reacting, and filtering to remove filtrate to obtain the demulsifier.
2. The method for preparing a demulsifier for hydrocarbon sewage according to claim 1, wherein in the step S1, the modified carrier contains amino groups, the molar ratio of the amino groups to the acrylic acid is 1:1, and the dosage of the p-toluenesulfonic acid is 5% of the mass of the acrylic acid.
3. The method for preparing a demulsifier for hydrocarbon sewage according to claim 1, wherein in the step S2, the mass ratio of the functionalized carrier, the modifier and the methacryloyloxyethyl trimethyl ammonium chloride is 1:52:6, and the amount of potassium persulfate is 1-1.5% of the mass of the methacryloyloxyethyl trimethyl ammonium chloride.
4. The method for preparing the demulsifier for hydrocarbon sewage according to claim 1, wherein the modifier is prepared by the following steps:
step A1: mixing and stirring perfluorooctyl methyl dimethoxy silane, dodecyl methyl dimethoxy silane and deionized water, adding concentrated sulfuric acid and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, reacting, and regulating pH to be neutral to obtain diamine-terminated polysiloxane;
step A2: dissolving methyl acrylate in methanol, adding sodium hydroxide, introducing nitrogen for protection, stirring, adding ethylenediamine, heating for reaction to obtain an intermediate 1, adding diamine-terminated polysiloxane, continuing reaction to obtain hyperbranched amine, and mixing hyperbranched amine, acrylic acid, DCC and toluene for reaction to obtain the modifier.
5. The method for preparing demulsifier for hydrocarbon sewage according to claim 4, wherein the dosage ratio of perfluorooctylmethyldimethoxysilane, dodecylmethyldimethoxysilane, deionized water and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane in step A1 is 5mmol:2mmol:10mL:5mmol, and concentrated sulfuric acid is 8-10% of the sum of perfluorooctylmethyldimethoxysilane, dodecylmethyldimethoxysilane and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane.
6. The method for preparing a demulsifier for hydrocarbon sewage according to claim 4, wherein the molar ratio of methyl acrylate to ethylenediamine in the step A2 is 1:4, the molar ratio of the intermediate 1 to the diamine-terminated polysiloxane is n (3n+1), n is a natural number greater than 0, the hyperbranched amine contains an amino group, and the molar ratio of the amino group, acrylic acid and DCC is 1:1:1.2.
7. The method for preparing the demulsifier for hydrocarbon sewage according to claim 1, wherein the modified carrier is prepared by the following steps:
step B1: dispersing ferroferric oxide in deionized water, adding isopropanol, stirring, adding tetraethoxysilane, reacting, filtering to remove filtrate, dispersing a substrate in ethanol, adding deionized water, carrying out reflux treatment, filtering and drying to obtain a pretreated carrier;
step B2: dispersing the pretreated carrier in ethanol, adding deionized water, mixing and stirring, adding KH550, reacting, filtering to remove filtrate, dispersing the substrate in DMF, adding potassium hydroxide and propylene oxide, reacting, adding ethylene oxide, continuing reacting, filtering to remove filtrate, and obtaining the modified carrier.
8. The method for preparing a demulsifier for hydrocarbon sewage according to claim 7, wherein the dosage ratio of ferroferric oxide, deionized water, isopropyl alcohol and ethyl orthosilicate in the step B1 is 1.25g:50mL:100mL:2mL, and the dosage ratio of substrate, ethanol and deionized water is 80mg:14mL:1mL.
9. The method for preparing a demulsifier for hydrocarbon sewage according to claim 7, wherein the pretreatment carrier, ethanol, deionized water and KH550 in the step B2 are in a mass ratio of 100mg:50mL:5mL:0.2mL, the mass ratio of substrate, propylene oxide and ethylene oxide is 1:69:34.5, and the mass sum of propylene oxide and ethylene oxide is 15-20%.
10. A demulsifier for hydrocarbon sewage, characterized in that it is prepared by the method according to any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116603514A (en) * | 2023-07-18 | 2023-08-18 | 湖南亿康环保科技有限公司 | Sewage treatment agent for treating groundwater pollution and preparation method thereof |
| CN117205901A (en) * | 2023-11-08 | 2023-12-12 | 山东春帆环境科技有限责任公司 | Biological carbon recyclable sewage treatment agent and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116603514A (en) * | 2023-07-18 | 2023-08-18 | 湖南亿康环保科技有限公司 | Sewage treatment agent for treating groundwater pollution and preparation method thereof |
| CN116603514B (en) * | 2023-07-18 | 2023-11-14 | 湖南亿康环保科技有限公司 | Sewage treatment agent for treating groundwater pollution and preparation method thereof |
| CN117205901A (en) * | 2023-11-08 | 2023-12-12 | 山东春帆环境科技有限责任公司 | Biological carbon recyclable sewage treatment agent and preparation method thereof |
| CN117205901B (en) * | 2023-11-08 | 2024-01-16 | 山东春帆环境科技有限责任公司 | Biological carbon recyclable sewage treatment agent and preparation method thereof |
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