CN116751605A - Demulsifier for oily sewage treatment and preparation method thereof - Google Patents
Demulsifier for oily sewage treatment and preparation method thereof Download PDFInfo
- Publication number
- CN116751605A CN116751605A CN202310628170.3A CN202310628170A CN116751605A CN 116751605 A CN116751605 A CN 116751605A CN 202310628170 A CN202310628170 A CN 202310628170A CN 116751605 A CN116751605 A CN 116751605A
- Authority
- CN
- China
- Prior art keywords
- demulsifier
- ethylene oxide
- pressure
- oil
- addition reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010865 sewage Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 37
- FBCHMEOPUKIZJN-UHFFFAOYSA-N dodecyl 2-aminopropanoate;sodium Chemical compound [Na].CCCCCCCCCCCCOC(=O)C(C)N FBCHMEOPUKIZJN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000007259 addition reaction Methods 0.000 claims abstract description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 78
- 238000006243 chemical reaction Methods 0.000 description 71
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 63
- 229910052757 nitrogen Inorganic materials 0.000 description 39
- 238000010926 purge Methods 0.000 description 39
- 239000003921 oil Substances 0.000 description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 20
- 230000001105 regulatory effect Effects 0.000 description 19
- 238000001816 cooling Methods 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- 239000010779 crude oil Substances 0.000 description 13
- 238000004321 preservation Methods 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000013527 degreasing agent Substances 0.000 description 4
- 238000005237 degreasing agent Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000011206 ternary composite Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- -1 polyoxypropylene Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- MIROPXUFDXCYLG-UHFFFAOYSA-N pyridine-2,5-diamine Chemical compound NC1=CC=C(N)N=C1 MIROPXUFDXCYLG-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- YZUSQFBZRVWGAA-UHFFFAOYSA-M sodium 2-chlorododecanoate Chemical compound ClC(C(=O)[O-])CCCCCCCCCC.[Na+] YZUSQFBZRVWGAA-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- TXBCHPGETQLSGV-UHFFFAOYSA-M sodium;2-(dodecylamino)propanoate Chemical compound [Na+].CCCCCCCCCCCCNC(C)C([O-])=O TXBCHPGETQLSGV-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to the technical field of water treatment, and particularly relates to a demulsifier for treating oily sewage and a preparation method thereof. Under the condition of first high temperature and high pressure, under the action of a catalyst, sodium dodecyl aminopropionate and epoxypropane undergo an addition reaction to obtain a glycidyl ether intermediate; secondly, adding first ethylene oxide to perform addition reaction to obtain a mixed embedded ether intermediate; finally, under the second high-temperature and high-pressure condition, adding second ethylene oxide to perform addition reaction in an acidic environment. The demulsifier has the characteristics of simple synthesis process and high demulsification rate, and the oil removal rate reaches more than 98% when the use concentration is 15 mg/L.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a demulsifier for treating oily sewage and a preparation method thereof.
Background
Since the oil field enters the development period of high water content, a ternary composite flooding technology is developed for improving the crude oil recovery ratio, and the crude oil recovery ratio is obviously improved. However, the oil displacement agent alkali, the surfactant and the polymer also cause serious emulsification of oil field sewage, crude oil is extracted in a way of emulsion, the oil content in the extracted water is increased sharply, and the emulsion not only causes a series of difficulties for crude oil extraction, but also has adverse effects on oil gas gathering, processing and refining; and environmental resources are wasted, so that demulsification of sewage is needed to recover crude oil.
The process of separating emulsified water from crude oil is called demulsification and dehydration. The method for demulsification and dehydration of crude oil comprises an electric dehydration method, a wetting coalescence dehydration method, a chemical demulsification method and the like. The chemical demulsification method is a method commonly adopted in crude oil dehydration, and is to add a demulsifier into crude oil emulsion to break the emulsified state of the crude oil emulsion so as to separate oil and water into two layers, wherein the main component of the demulsifier is a surfactant.
The conventional demulsifier has more varieties and mainly comprises cationic organic high-molecular coagulants (such as polydimethyl diallyl ammonium chloride, epichlorohydrin-fatty amine and the like) and nonionic organic high-molecular coagulants (such as ethylene oxide-propylene oxide series), and the agents are commonly high in oil content of lower water after demulsification, so that the cost and difficulty of a later-stage sewage treatment system are increased.
CN101357783a discloses a preparation method of a high-efficiency emulsion breaker for emulsifying wastewater, which is characterized by comprising the following steps: in the first step, fe-containing 2 O 3 Adding 9-15% ferric salt aqueous solution and 0.8-2.4% sodium silicate aqueous solution containing silicon into ferric salt aqueous solution slowly according to the weight ratio of 10:1, and reacting at the temperature of 40-70 ℃ for 2-4 hours at the pH of 3-5 to obtain ferrosilicon polymer; in the second step, the same weight of the aqueous solution of the ferric salt as that of the aqueous solution of the ferric salt contains Al 2 O 3 Adding 10-14% trivalent aluminum salt aqueous solution into the iron-silicon polymer synthesized in the first step under stirring, adjusting the pH to 2-3.5, and polymerizing at 40-70 ℃ for 2-4h to obtain the demulsifier. The emulsion breaking agent for the emulsified wastewater has the functions of coagulation and purification, convenient operation and good environmental protection performance. However, when the degreasing agent is used for treating sewage, a large amount of scum can be generated, secondary pollution is caused, and the degreasing effect is difficult to ensure.
CN106565007 discloses a degreasing agent for ternary composite flooding produced water, which is prepared by reacting 2, 5-pyridine diamine with formaldehyde and formic acid to generate an intermediate, and then reacting with sodium chlorododecanoate to generate a zwitterionic degreasing agent, wherein the 2, 5-pyridine diamine, formaldehyde and formic acidAnd sodium chlorododecanoate in the molar ratio of 1:2.5-6:2.5-5.5:0.8-2.5, preferably 1:3:3:1.5. The degreasing agent has the characteristics of simple preparation, strong adaptability, low cost, strong salt resistance and good degreasing effect, and the salt resistance reaches 2.3X10 4 mg/L, the oil removal rate of the ternary complex flooding produced water reaches more than 97%. And the recovered oil produced by separation does not influence the subsequent crude oil dehydration, so the invention can be widely applied to the oil removal process of the ternary composite flooding produced water. However, the product of the invention contains pyridine monomer, which has high toxicity and is easy to cause environmental pollution.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a demulsifier for treating oily sewage and a preparation method thereof.
In order to achieve the above purpose, the first purpose of the present invention is to disclose a demulsifier for treating oily sewage, wherein the molecular formula of the demulsifier is as follows:
wherein:
m is a positive integer from 2 to 50, preferably from 20 to 50.
n is a positive integer from 2 to 50, preferably from 10 to 50.
l is a positive integer from 2 to 50, preferably from 10 to 50.
Another object of the present invention is to provide a method for preparing the demulsifier for treating oily sewage, which comprises the following steps: under the first high-temperature and high-pressure condition, under the action of a catalyst, sodium dodecyl aminopropionate and propylene oxide undergo an addition reaction to obtain a glycidyl ether intermediate; secondly, adding first ethylene oxide to perform addition reaction to obtain a mixed embedded ether intermediate; finally, under the condition of second high temperature and high pressure, adding second ethylene oxide to perform addition reaction, wherein the structural formula of the embedded propyl ether intermediate is shown as a formula (1), the structural formula of the mixed embedded ether intermediate is shown as a formula (2),
wherein: m is a positive integer from 2 to 50, preferably a positive integer from 20 to 50; n is a positive integer from 2 to 50, preferably from 10 to 50.
In the present invention, preferably, the molar ratio of the propylene oxide, the first ethylene oxide and the sodium dodecyl aminopropionate is 2 to 50:2-50:1, a step of; more preferably, the molar ratio of the propylene oxide, the first ethylene oxide and the sodium dodecyl aminopropionate is 10 to 50:5-50:1.
in the present invention, preferably, the molar ratio of the second ethylene oxide to the sodium dodecylaminopropionate is 2 to 50:1, a step of; more preferably, the molar ratio of the second ethylene oxide to the sodium dodecyl aminopropionate is 5-50:1.
in the invention, preferably, the catalyst is sodium hydroxide or potassium hydroxide, and the mass ratio of the catalyst to the sodium dodecyl aminopropionate is 0.005-0.05:1.
in the present invention, preferably, the first high temperature and high pressure condition is a temperature of 120-160 ℃ and a pressure of 0.05-0.3MPa.
In the present invention, it is preferable that the time of the propylene oxide addition reaction is 0.5 to 4 hours.
In the present invention, it is preferable that the time of the first ethylene oxide addition reaction is 0.5 to 4 hours.
In the present invention, preferably, the acidic environment is a pH of 3 to 4.
In the present invention, preferably, the second high temperature and high pressure condition is a temperature of 130-170 ℃ and a pressure of 0.05-0.4MPa.
In the present invention, it is preferable that the time of the second ethylene oxide addition reaction is 0.5 to 6 hours.
According to a more specific preferred embodiment, the preparation method of the demulsifier for treating the oily sewage specifically comprises the following steps:
(1) Adding sodium dodecyl aminopropionate, toluene and a catalyst into a high-pressure reaction kettle, purging the reaction kettle and a pipeline for 2-3min by using nitrogen, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, repeating the operation for 3 times, introducing propylene oxide, heating, raising the pressure, carrying out heat preservation reaction, introducing first ethylene oxide, adjusting the reaction temperature and the pressure, carrying out heat preservation reaction, cooling to below 40 ℃, and stopping the reaction;
(2) Opening the reaction kettle, regulating the pH value to 3-4 by using 1mol/L hydrochloric acid, filtering the reaction mixed solution, separating the solution, decompressing and distilling the toluene phase to obtain viscous liquid, and transferring the viscous liquid into the high-pressure kettle;
(3) And (3) purging the reaction kettle and the pipeline for 2-3min by using nitrogen, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, repeating the operation for 3 times, introducing second ethylene oxide, heating, raising the pressure, carrying out heat preservation reaction, cooling to below 40 ℃, and regulating the pH value to 7-8 by using 1mol/L sodium hydroxide to obtain the product demulsifier.
Preferably, in the step (1), the mass ratio of toluene to sodium dodecyl aminopropionate is 3-5:1.
the reaction equation of the demulsifier of the invention is:
the demulsifier is a weak positive nonionic surfactant, the lipophilic group is dodecyl and a polyoxypropylene ether segment, and the hydrophilic group is 2 polyoxyethylene ether segments and tertiary amine. Most of crude oil in oilfield produced water exists in the form of O/W emulsion, most of the crude oil is tiny oil drops, and the surfaces of the oil drops are negatively charged and very stable. The tertiary amine can neutralize the oil drops with negative charges, so that the oil drops lose repulsive interaction to be mutually aggregated, and tiny oil drops are aggregated and released to achieve a demulsification effect; the molecules of the invention can enter an oil-water interface to replace a surfactant with strong emulsifying property, and replace the surfactant molecules and other surface active substances, thereby reducing the stability of the interface film, destroying the emulsifying capacity of oil drops and enabling the oil drops to be more easily condensed so as to realize oil-water separation; the polyether segment in the molecule can sweep a large amount of tiny oil drops, has high flexibility, is easy to rotate in a molecular chain, increases the collision opportunity of the oil drops, and forms the oil drops which are easy to aggregate and float upwards to achieve the purpose of demulsification.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The demulsifier has the characteristics of low raw material price, wide sources and simple synthesis process;
(2) The demulsifier has good demulsification effect, and the oil removal rate reaches more than 98% when the use concentration is 15 mg/L.
Drawings
FIG. 1 shows a demulsifier N for products according to the invention 7 An infrared spectrum characterization map.
Detailed Description
The invention will be described in further detail below with reference to specific examples and with reference to the data. It should be understood that these examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
Example 1
(1) Adding 0.5mol of sodium dodecyl aminopropionate, 483g of toluene and 0.7g of sodium hydroxide into a high-pressure reaction kettle, purging the reaction kettle and a pipeline for 2min by using nitrogen, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, repeating the operation for 3 times, introducing 1mol of propylene oxide, heating to 120 ℃, keeping the pressure to 0.05MPa, reacting for 1h, introducing 1mol of ethylene oxide, adjusting the reaction temperature to 125 ℃, keeping the pressure to 0.05MPa, reacting for 0.5h, cooling to below 40 ℃, and stopping the reaction.
(2) The reaction kettle is opened, the pH value is regulated to 3-4 by 1mol/L hydrochloric acid, the reaction mixture is filtered, separated, toluene phase is distilled under reduced pressure to obtain viscous liquid, and the viscous liquid is transferred into the autoclave.
(3) Purging the reaction kettle and the pipeline for 2min by using nitrogen, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, repeating the above operation for 3 times, and introducing 1moL ethylene oxide is heated to 130 ℃, the pressure is 0.05MPa, the temperature is kept for 0.5h, the temperature is reduced to below 40 ℃, 1mol/L sodium hydroxide is used for adjusting the pH value to 7-8, and the demulsifier N of the product is obtained 1 。
Example 2
(1) Adding 0.5mol of sodium dodecyl aminopropionate, 419g of toluene and 1.2g of sodium hydroxide into a high-pressure reaction kettle, purging the reaction kettle and a pipeline for 3min by using nitrogen, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, repeating the operation for 3 times, introducing 2mol of propylene oxide, heating to 120 ℃, keeping the pressure to 0.05MPa, reacting for 1h, introducing 5mol of ethylene oxide, adjusting the reaction temperature to 130 ℃, keeping the pressure to 0.05MPa, reacting for 0.5h, cooling to below 40 ℃, and stopping the reaction.
(2) The reaction kettle is opened, the pH value is regulated to 3-4 by 1mol/L hydrochloric acid, the reaction mixture is filtered, separated, toluene phase is distilled under reduced pressure to obtain viscous liquid, and the viscous liquid is transferred into the autoclave.
(3) Purging the reaction kettle and the pipeline for 2min by nitrogen, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, repeating the above operation for 3 times, introducing 5mol of ethylene oxide, heating to 135 ℃, keeping the pressure to 0.07MPa, carrying out heat preservation reaction for 1h, cooling to below 40 ℃, and regulating the pH value to 7-8 by using 1mol/L of sodium hydroxide to obtain the demulsifier N 2 。
Example 3
(1) Adding 0.5mol of sodium dodecyl aminopropionate, 492g of toluene and 2.8g of sodium hydroxide into a high-pressure reaction kettle, purging the reaction kettle and a pipeline for 2min by using nitrogen, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, repeating the operation for 3 times, introducing 5mol of propylene oxide, heating to 125 ℃, keeping the pressure to 0.1MPa, reacting for 0.5h, introducing 10mol of ethylene oxide, adjusting the reaction temperature to 140 ℃, keeping the pressure to 0.1MPa, reacting for 1h, cooling to below 40 ℃, and stopping the reaction.
(2) The reaction kettle is opened, the pH value is regulated to 3-4 by 1mol/L hydrochloric acid, the reaction mixture is filtered, separated, toluene phase is distilled under reduced pressure to obtain viscous liquid, and the viscous liquid is transferred into the autoclave.
(3) Purging the reaction kettle and the pipeline for 2min by using nitrogen, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, and repeatingThe operation is carried out for 3 times, 8mol of ethylene oxide is introduced, the temperature is raised to 140 ℃, the pressure is raised to 0.1MPa, the heat preservation reaction is carried out for 2 hours, the temperature is reduced to below 40 ℃, 1mol/L of sodium hydroxide is used for regulating the pH value to 7-8, and the demulsifier N is obtained 3 。
Example 4
(1) Adding 0.5mol of sodium dodecyl aminopropionate, 505g of toluene and 3.8g of sodium hydroxide into a high-pressure reaction kettle, purging the reaction kettle and a pipeline for 3min by using nitrogen, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, repeating the operation for 3 times, introducing 10mol of propylene oxide, heating to 125 ℃, keeping the pressure to 0.15MPa, reacting for 1h, introducing 15mol of ethylene oxide, adjusting the reaction temperature to 147 ℃, keeping the pressure to 0.1MPa, reacting for 1h, cooling to below 40 ℃, and stopping the reaction.
(2) The reaction kettle is opened, the pH value is regulated to 3-4 by 1mol/L hydrochloric acid, the reaction mixture is filtered, separated, toluene phase is distilled under reduced pressure to obtain viscous liquid, and the viscous liquid is transferred into the autoclave.
(3) Purging the reaction kettle and the pipeline for 2min by nitrogen, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, repeating the above operation for 3 times, introducing 20mol of ethylene oxide, heating to 148 ℃, maintaining the pressure to 0.2MPa, reacting for 3h, cooling to below 40 ℃, and regulating the pH to 7-8 by using 1mol/L sodium hydroxide to obtain the demulsifier N 4 。
Example 5
(1) Adding 0.5mol of sodium dodecyl aminopropionate, 620g of toluene and 4.5g of sodium hydroxide into a high-pressure reaction kettle, purging the reaction kettle and a pipeline for 2min by using nitrogen, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, repeating the operation for 3 times, introducing 15mol of propylene oxide, heating to 135 ℃, keeping the pressure to 0.15MPa, reacting for 2h, introducing 20mol of ethylene oxide, adjusting the reaction temperature to 150 ℃, keeping the pressure to 0.2MPa, reacting for 2h, cooling to below 40 ℃, and stopping the reaction.
(2) The reaction kettle is opened, the pH value is regulated to 3-4 by 1mol/L hydrochloric acid, the reaction mixture is filtered, separated, toluene phase is distilled under reduced pressure to obtain viscous liquid, and the viscous liquid is transferred into the autoclave.
(3) Purging the reaction kettle and the pipeline for 2min by nitrogen, stopping purging, vacuumizing, and introducing nitrogenAnd (3) vacuumizing, repeating the above operation for 3 times, introducing 25mol of ethylene oxide, heating to 155 ℃, maintaining the pressure to 0.28MPa, performing heat preservation reaction for 3 hours, cooling to below 40 ℃, and regulating the pH value to 7-8 by using 1mol/L of sodium hydroxide to obtain the demulsifier N 5 。
Example 6
(1) Adding 0.5mol of sodium dodecyl aminopropionate, 645g of toluene and 5.8g of sodium hydroxide into a high-pressure reaction kettle, purging the reaction kettle and a pipeline for 3min by using nitrogen, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, repeating the operation for 3 times, introducing 20mol of propylene oxide, heating to 140 ℃, keeping the pressure to 0.2MPa, carrying out heat preservation reaction for 3h, introducing 25mol of ethylene oxide, adjusting the reaction temperature to 152 ℃, keeping the pressure to 0.22MPa, carrying out heat preservation reaction for 3h, cooling to below 40 ℃, and stopping the reaction.
(2) The reaction kettle is opened, the pH value is regulated to 3-4 by 1mol/L hydrochloric acid, the reaction mixture is filtered, separated, toluene phase is distilled under reduced pressure to obtain viscous liquid, and the viscous liquid is transferred into the autoclave.
(3) Purging the reaction kettle and the pipeline for 3min by nitrogen, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, repeating the above operation for 3 times, introducing 25mol of ethylene oxide, heating to 170 ℃, maintaining the pressure to 0.4MPa, reacting for 6h, cooling to below 40 ℃, and regulating the pH to 7-8 by using 1mol/L sodium hydroxide to obtain the demulsifier N 6 。
Example 7
(1) Adding 0.5mol of sodium dodecyl aminopropionate, 633g of toluene and 7g of potassium hydroxide into a high-pressure reaction kettle, purging the reaction kettle and a pipeline for 2min by using nitrogen, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, repeating the operation for 3 times, introducing 25mol of propylene oxide, heating to 150 ℃, keeping the pressure to 0.28MPa, carrying out heat preservation for 4h, introducing 25mol of ethylene oxide, adjusting the reaction temperature to 160 ℃, keeping the pressure to 0.3MPa, carrying out heat preservation for 4h, cooling to below 40 ℃, and stopping the reaction.
(2) The reaction kettle is opened, the pH value is regulated to 3-4 by 1mol/L hydrochloric acid, the reaction mixture is filtered, separated, toluene phase is distilled under reduced pressure to obtain viscous liquid, and the viscous liquid is transferred into the autoclave.
(3) The reaction kettle and the pipeline are purged by nitrogen for 2min, and the purging is stoppedVacuumizing, introducing nitrogen, vacuumizing, repeating the above operation for 3 times, introducing 25mol of ethylene oxide, heating to 165 ℃, maintaining the pressure to 0.38MPa, performing heat preservation reaction for 6 hours, cooling to below 40 ℃, and regulating the pH to 7-8 by using 1mol/L of sodium hydroxide to obtain the demulsifier N 7 。
Example 8
(1) Adding 0.5mol of sodium dodecyl aminopropionate, 697g of toluene and 6.5g of potassium hydroxide into a high-pressure reaction kettle, purging the reaction kettle and a pipeline for 2min by nitrogen, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, repeating the operation for 3 times, introducing 25mol of propylene oxide, heating to 150 ℃, keeping the pressure to 0.3MPa, reacting for 4h, introducing 20mol of ethylene oxide, adjusting the reaction temperature to 158 ℃, keeping the pressure to 0.3MPa, reacting for 4h, cooling to below 40 ℃, and stopping the reaction.
(2) The reaction kettle is opened, the pH value is regulated to 3-4 by 1mol/L hydrochloric acid, the reaction mixture is filtered, separated, toluene phase is distilled under reduced pressure to obtain viscous liquid, and the viscous liquid is transferred into the autoclave.
(3) Purging the reaction kettle and the pipeline for 3min by nitrogen, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, repeating the above operation for 3 times, introducing 20mol of ethylene oxide, heating to 165 ℃, keeping the pressure to 0.35MPa, carrying out heat preservation reaction for 5h, cooling to below 40 ℃, and regulating the pH value to 7-8 by using 1mol/L of sodium hydroxide to obtain the product demulsifier N 8 。
Example 9
(1) Adding 0.5mol of sodium dodecyl aminopropionate, 685g of toluene and 6.2g of potassium hydroxide into a high-pressure reaction kettle, purging the reaction kettle and a pipeline for 2min by using nitrogen, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, repeating the operation for 3 times, introducing 25mol of propylene oxide, heating to 150 ℃, keeping the pressure to 0.3MPa, reacting for 4h, introducing 15mol of ethylene oxide, adjusting the reaction temperature to 156 ℃, keeping the pressure to 0.28MPa, reacting for 4h, cooling to below 40 ℃, and stopping the reaction.
(2) The reaction kettle is opened, the pH value is regulated to 3-4 by 1mol/L hydrochloric acid, the reaction mixture is filtered, separated, toluene phase is distilled under reduced pressure to obtain viscous liquid, and the viscous liquid is transferred into the autoclave.
(3) Nitrogen purging of the reactorPipeline for 3min, stopping purging, vacuumizing, introducing nitrogen, vacuumizing, repeating the above operation for 3 times, introducing 20mol of ethylene oxide, heating to 162 ℃, maintaining the pressure to 0.32MPa, reacting for 5h, cooling to below 40 ℃, and regulating pH to 7-8 with 1mol/L sodium hydroxide to obtain the demulsifier N 9 。
Example 10 demulsifier house evaluation
The demulsification experiment is carried out on ternary composite flooding produced water of a certain oil field, the oil content is 1450mg/L, the experimental method refers to the method for evaluating the use performance of an oil-in-water emulsion demulsifier of SY/T5797-1993, and the demulsifier AES (polyoxyethylene sodium nonylphenol sulfate) is used for comparison experiments, and the experimental results are shown in Table 1.
TABLE 1 demulsification test results (oil removal rate,%)
As can be seen from table 1:
(1) Demulsifier N of the invention 1 -N 9 The oil removal rate reaches 85% or more when the using concentration is 5mg/L, and the maximum oil removal rate reaches 94.7%; while the oil removal rate of AES is 78.8% when the use concentration is 5 mg/L;
(2) Demulsifier N of the invention 1 -N 9 The oil removal rate reaches 90% or more when the using concentration is 10mg/L, and reaches 97.6% at most; while the oil removal rate of AES is 86.6% when the use concentration is 10 mg/L;
(3) Demulsifier N of the invention 1 -N 9 The oil removal rate reaches 98% or above when the using concentration is 15mg/L, and the maximum oil removal rate reaches 99.2%; while the oil removal rate of AES was 92.3% at a use concentration of 15 mg/L.
Compared with the prior art, the demulsifier has good oil removal effect.
Example 11 demulsifier in situ application
Combined station L 4 The water is oil field binary drive produced water, and is in a combined station L 4 Performing field test with test treatment scale of 120m 3 And/d, the oil content of the incoming water is 1320mg/L, the mineralization degree of the produced water is 18900mg/L, and the temperature is 68 ℃. Demulsifier N using the present invention 7 To a combined station L 4 Demulsification treatment is carried out on the produced water of (2) demulsifier N 7 The addition amount of the oil is 1.8kg/d, the concentration is 15mg/L, the oil content of the treated produced water is reduced to 23.76mg/L, the oil removal rate reaches 98.2%, and the process requirement is met.
Example 12 characterization of Infrared Spectroscopy
Product N is subjected to infrared spectrum 7 Characterization was performed and the results are shown in fig. 1.
In FIG. 1, 2942cm -1 Is the C-H bond absorption peak in dodecyl; 1343cm -1 Is a C-N bond absorption peak; 1360cm -1 Is the absorption peak of the polyoxypropylene ether segment; 1112cm -1 Is the absorption peak of the polyoxyethylene ether segment.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The preparation method of the demulsifier for treating the oily sewage is characterized by comprising the following steps of: under the first high-temperature and high-pressure condition, under the action of a catalyst, sodium dodecyl aminopropionate and propylene oxide undergo an addition reaction to obtain a glycidyl ether intermediate; secondly, adding first ethylene oxide to perform addition reaction to obtain a mixed embedded ether intermediate; finally, under the condition of second high temperature and high pressure, adding second ethylene oxide to perform addition reaction, wherein the structural formula of the embedded propyl ether intermediate is shown as a formula (1), the structural formula of the mixed embedded ether intermediate is shown as a formula (2),
wherein: m is a positive integer of 2-50, n is a positive integer of 2-50;
the mol ratio of the propylene oxide to the first ethylene oxide to the sodium dodecyl aminopropionate is 2-50:2-50:1.
2. the method for preparing the demulsifier for treating oily sewage according to claim 1, wherein the molar ratio of the propylene oxide to the first ethylene oxide to the sodium dodecyl aminopropionate is 10-50:5-50:1.
3. the method for preparing the demulsifier for treating oily sewage according to claim 1, wherein the molar ratio of the second ethylene oxide to the sodium dodecyl aminopropionate is 2-50:1.
4. the method for preparing the demulsifier for treating oily sewage according to claim 1, wherein the catalyst is sodium hydroxide or potassium hydroxide and the mass ratio of the catalyst to the sodium dodecyl aminopropionate is 0.005-0.05:1.
5. the method for preparing a demulsifier for oil-containing sewage treatment according to claim 1, wherein the first high temperature and high pressure condition is that the temperature is 120-160 ℃ and the pressure is 0.05-0.3MPa.
6. The method for preparing a demulsifier for oil-containing sewage treatment according to claim 1, wherein the time of the propylene oxide addition reaction is 0.5-4h.
7. The method for preparing a demulsifier for oil-containing sewage treatment according to claim 1, wherein the time of the first ethylene oxide addition reaction is 0.5-4 hours.
8. The method for preparing a demulsifier for oil-containing sewage treatment according to claim 1, wherein the second high-temperature and high-pressure condition is that the temperature is 130-170 ℃ and the pressure is 0.05-0.4MPa.
9. The method for preparing a demulsifier for oil-containing sewage treatment according to claim 1, wherein the time of the second ethylene oxide addition reaction is 0.5-6h.
10. The demulsifier for treating the oily sewage is characterized by comprising the following molecular formula:
wherein:
m is a positive integer of 2-50;
n is a positive integer from 2 to 50;
l is a positive integer of 2-50.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310628170.3A CN116751605A (en) | 2023-05-29 | 2023-05-29 | Demulsifier for oily sewage treatment and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310628170.3A CN116751605A (en) | 2023-05-29 | 2023-05-29 | Demulsifier for oily sewage treatment and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116751605A true CN116751605A (en) | 2023-09-15 |
Family
ID=87946936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310628170.3A Pending CN116751605A (en) | 2023-05-29 | 2023-05-29 | Demulsifier for oily sewage treatment and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116751605A (en) |
-
2023
- 2023-05-29 CN CN202310628170.3A patent/CN116751605A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110240369B (en) | Pyrolysis-extraction circulating recycling treatment process method for polymer-containing oil sludge | |
| CN107973506B (en) | Demulsifier for conditioning and three-phase separation of oily sludge and preparation method thereof | |
| CN106866954A (en) | A kind of cation polyether reverse-phase emulsifier and preparation method thereof | |
| CN102476877A (en) | Silicon-removing and oil-removing composite method of oil-containing sewage for boiler reuse | |
| CN106497600A (en) | A kind of offshore oilfield Produced Liquid comprehensive treatment agent and preparation method thereof | |
| CN105295017B (en) | A kind of low temperature crude oil demulsifier and preparation method thereof | |
| CN1966138A (en) | Highly efficient anti-phase emulsion breaker for thick oil pollution water processing | |
| CN102899070B (en) | Binary flooding produced liquid comprehensive treatment agent and preparation method | |
| CN108277041B (en) | Water-soluble demulsifier for gas field exploitation and transportation, and preparation method and application thereof | |
| CN116751605A (en) | Demulsifier for oily sewage treatment and preparation method thereof | |
| WO2020258358A1 (en) | Three-dimensional crude oil demulsifier, preparation method therefor, and application thereof | |
| CN107235529A (en) | A kind of degreaser handled for oil-contaminated water of oil field and preparation method thereof | |
| CN108773978A (en) | A kind of organic silicon wastewater processing system and its processing method | |
| CN112979115B (en) | Rapid gel breaker for treating xanthan gum system oil sludge emulsion and preparation method and application thereof | |
| CN102559244A (en) | Demulsifying and water-purifying agent for treating produced liquid of polymer injecting area and preparation method thereof | |
| CN115558096A (en) | Comb-type cardanol polyether demulsifier, and preparation method and application thereof | |
| JP6306819B2 (en) | Water-in-oil emulsion composition and method for producing and using the same | |
| CN110643340B9 (en) | High-efficiency water-soluble viscosity-reduction oil washing agent for heavy oil thermal recovery and preparation method thereof | |
| CN111056593B (en) | Fluoropolyether-containing thick oil water purifier | |
| CN111718745B (en) | Macromolecule crude oil demulsifier | |
| CN113121812A (en) | Water purifier for treating oily sewage in oil field and preparation method and application thereof | |
| CN114516976B (en) | Pretreatment process for hydrolysis waste of dimethyl dichlorosilane | |
| CN114426829B (en) | Viscosity reducer for thick oil steam huff and puff exploitation and preparation method thereof | |
| CN103113571B (en) | Preparation method of demulsifier polyether intermediate compound | |
| CN110387255A (en) | A kind of non-ionic water-soluble heavy crude desalination demulsifier and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |