CN106749123B - A kind of degreaser and preparation method thereof of the binary of quaternary amine containing heterocycle combination flooding sewage - Google Patents
A kind of degreaser and preparation method thereof of the binary of quaternary amine containing heterocycle combination flooding sewage Download PDFInfo
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- CN106749123B CN106749123B CN201611023765.2A CN201611023765A CN106749123B CN 106749123 B CN106749123 B CN 106749123B CN 201611023765 A CN201611023765 A CN 201611023765A CN 106749123 B CN106749123 B CN 106749123B
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- 239000013527 degreasing agent Substances 0.000 title claims abstract description 74
- 239000010865 sewage Substances 0.000 title claims abstract description 39
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 21
- 125000003277 amino group Chemical group 0.000 title 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 42
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001348 alkyl chlorides Chemical class 0.000 claims abstract description 16
- UTVVREMVDJTZAC-UHFFFAOYSA-N furan-2-amine Chemical compound NC1=CC=CO1 UTVVREMVDJTZAC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001412 amines Chemical group 0.000 claims abstract description 12
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- 239000003921 oil Substances 0.000 abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 20
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000010779 crude oil Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 239000011218 binary composite Substances 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 0 **(CC(CCCCC1)C1=O)Cc1ccc[n]1 Chemical compound **(CC(CCCCC1)C1=O)Cc1ccc[n]1 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Detergent Compositions (AREA)
- Lubricants (AREA)
Abstract
The invention belongs to disposing polluted water in oil technical fields, more particularly to a kind of degreaser of the binary of quaternary amine containing heterocycle combination flooding sewage, the degreaser is to obtain Minnich alkali by condensation reaction by 2- furylamine, formaldehyde and cyclohexanone, then reacts acquisition with alkyl chloride again；2- furylamine, formaldehyde, cyclohexanone and alkyl chloride molar ratio be 1:5~8:1.5~2:3~5, preferably 1:7:1.8:4.5.Degreaser of the invention, which has, prepares simple, adaptable, at low cost, oil removal rate up to 95% or more；And the oil recovery that separation generates does not influence subsequent crude oil dehydration, therefore, present invention is generally applicable in the oil removing process of binary combination flooding output water.
Description
Technical field
The invention belongs to technical field of sewage, and in particular to a kind of binary combination flooding sewage of quaternary amine containing heterocycle removes
Finish and preparation method thereof.
Background technique
The most of late high water content period that all enters in east China major part oil field is widely used to improve oil recovery factor
The tertiary oil recovery new technology of polymer flooding technique and binary combination flooding (polymer and surfactant).Binary combination flooding
Tar productivity can be significantly improved, is had broad application prospects, but due to gathering in binary composite-driven produced water containing a large amount of
Acrylamide and surfactant cause the viscosity of sewage to become larger, and Oil in Sewage Water bead diameter becomes smaller, and cause sewage emulsification tight
Weight, processing difficulty are larger.
Conventional treatment process (natural subsidence-coagulant precipitation-filtering) is difficult to obtain binary composite-driven produced water at present
It is effectively treated.Another method for removing oil field binary combination flooding output water Crude Oil is chemical method, that is, uses oil removing agent method.
Degreaser is broadly divided into following two categories, and element of the first species's multiplicity, deoiling effect is good, but there is preparation process complexity, anti-salt property
The shortcomings that difference, higher cost；Another kind of degreaser ingredient is single, and preparation method and technique are relatively simple, the requirement to water quality compared with
It is low, but have the shortcomings that deoiling effect is poor.
Patent ZL201410254042.8 " a kind of composite flocculation deoiling agent for oily waste water treatment " uses sulfuric acid
Aluminium, magnesium chloride, magnesium hydroxide, bentonite and polyacrylamide are combined, which has dosage few, and oil removal efficiency is high,
The features such as preparation is simple, at low cost, but degreaser needs are used with corrosive magnesium hydroxide, the compound is to equipment
With stronger corrosiveness.A large amount of magnesium ion and aluminium ion are used in the invention simultaneously, with polymerizeing in binary combination flooding
Object or surfactant are easy to happen reaction, generate precipitating, it is difficult to apply in the processing of binary composite-driven produced water.
Summary of the invention
The present invention provides a kind of degreaser of the binary of quaternary amine containing heterocycle combination flooding sewage in view of the deficiencies of the prior art
And preparation method thereof, the present invention has simple process, low in cost, and the feature that deoiling effect is good, and it is multiple to be suitable for oil field binary
Close the oil removing for driving output sewage.
The invention discloses a kind of degreaser of the binary of quaternary amine containing heterocycle combination flooding sewage, which is by 2- furans
Methylamine, formaldehyde and cyclohexanone obtain Minnich alkali by condensation reaction, then react acquisition with alkyl chloride again, molecular formula is such as
Under:
Wherein R is C12-C18Linear paraffin, preferably C16Linear paraffin.
The 2- furylamine, formaldehyde, cyclohexanone and alkyl chloride molar ratio be 1:5~8:1.5~2:3~5, preferably
For 1:7:1.8:4.5.
It is a further object to provide a kind of preparations of the degreaser of the binary of quaternary amine containing heterocycle combination flooding sewage
Method, the preparation method the following steps are included:
(1) the 2- furan of above-mentioned molar ratio is added in the three-necked flask that electric mixer, reflux condensing tube, thermometer are housed
It mutters methylamine, etoh solvent is then added, the additional amount of ethyl alcohol is 10~15 times of 2- furylamine mole, is warming up to 40~50
DEG C, 10~30min is stirred in the case where stirring rate is 200~300rpm, the cyclohexanone of aforementioned proportion is then added, temperature rises to 60
~70 DEG C, stirring rate be 300~400rpm, persistently stir 20~30min after be cooled to 30~35 DEG C, then with 15% salt
Acid for adjusting pH value obtains mixture A to 2~5；
(2) constant pressure funnel is put into after mixing the formaldehyde of above-mentioned molar ratio according to the molar ratio of 1:1.2 with ethyl alcohol
In, the temperature of mixture A is adjusted to 60~70 DEG C, and the formaldehyde in constant pressure funnel is added drop-wise to the mixture of ethyl alcohol and is mixed
In object A, stir when being added dropwise, rate of addition is 2~3 drops/min, and stirring rate is 300~500rpm, after 3~5h of isothermal reaction
It is naturally cooling to room temperature and obtains solution B；
(3) for solution B in the case where stirring rate is 200~300rpm, temperature is adjusted to 40~50 DEG C, and above-mentioned molar ratio is added
Alkyl chloride then heats to 80~90 DEG C, and stirring rate is adjusted to 300~400rpm, then constant temperature 3~7h of back flow reaction cools down
The reaction was continued after to 40~50 DEG C 1~3h, obtains mixture C；
(4) mixture C is cooled to room temperature, be then transferred in round-bottomed flask, vacuum distillation removes solvent and excessive
Formaldehyde, then place into vacuum oven dry 12~for 24 hours, obtain degreaser of the invention.
The reaction equation is as follows:
A kind of degreaser of the binary of quaternary amine containing heterocycle combination flooding sewage, as follows using technical process:
According to oil-containing situation in the binary combination flooding output sewage of oil field, degreaser of the invention is added into sewage, realizes
Demulsification and water-oil separating are further processed after recycling petroleum substance for subsequent technique.The specific additional amount of degreaser is as follows:
(1) when oil-containing α >=500mg/L, degreaser, which is added, makes 60~100mg/L of mass concentration of degreaser in sewage；
When (2) 500 ﹥ oil-containing α >=200mg/L, degreaser, which is added, makes 30~50mg/ of mass concentration of degreaser in sewage
L；
When (3) 200 ﹥ oil-containing α >=50mg/L, degreaser, which is added, makes 10~20mg/ of mass concentration of degreaser in sewage
L；
(4) when oil-containing α < 50mg/L, degreaser, which is added, makes 0.1~10mg/L of mass concentration of degreaser in sewage.
The present invention is provided to the degreaser of oil field binary combination flooding output sewage oil removing, hydrophobic long-chains, heterocyclic group
With cycloalkane on a N atom, wherein lipophilic group and heterocyclic group can be adsorbed onto rapidly on the oil in sewage；Naphthenic base
Polarity it is lower, micella is easily formed, so additive amount is low；Positively charged ammonium ion is easy to be adsorbed onto the surface of greasy dirt,
And across 2~3 noncoordinating atoms between oxygen, nitrogen and nitrogen, nitrogen, the lone pair electrons of coordination atom enter the presence in greasy dirt
Hydridization dsp unoccupied orbital, form coordinate bond, it is prone to which complexing, the flocculation for promoting greasy dirt increases, and then improves pair
Oilfield sewage oil removal treatment effect.
The present invention is had the following advantages and beneficial effects: compared with prior art
(1) raw material sources of degreaser of the invention are extensive, and synthesis technology is simple, and product is easily obtained and transports preservation；
(2) degreaser of the invention is adaptable, and dosage is few, can meet the needs of environmental protection and oil field development
(3) degreaser of the invention does not contain inorganic flocculation ingredient, and the flocculation ability of the ability that is demulsified and greasy dirt is stronger, point
The dehydration of normal crude oil is had little effect from the oil recovery of generation；
(4) degreaser of the invention has the characteristics that oil removal efficiency is high, and the oil removal rate of binary composite-driven produced water is up to 95%
More than, more existing medicament improves 40% or more, meets the pretreated requirement of oil removing of binary combination flooding oily wastewater.
Specific embodiment
The present invention is described in further detail below with reference to specific embodiment, and referring to data.It should be understood that these embodiments
It is of the invention solely for the purpose of illustration, rather than limit the scope of the invention in any way.
Specific embodiment
The present invention is described in further detail below with reference to specific embodiment, and referring to data.It should be understood that these embodiments
It is of the invention solely for the purpose of illustration, rather than limit the scope of the invention in any way.
Embodiment 1: degreaser P1And preparation method thereof
(1) degreaser P1Composition, component and molecular formula it is as follows:
Degreaser P1It is anti-for 1:5:1.5:3.0 ratio according to molar ratio by 2- furylamine, formaldehyde, cyclohexanone and alkyl chloride
It should obtain, molecular formula is as follows:
Wherein R is C12Linear paraffin.
(2) degreaser P1The preparation method is as follows:
1. the 2- furylamine of 1mol is added in the three-necked flask that electric mixer, reflux condensing tube, thermometer are housed,
Then solvent 15mol ethyl alcohol is added, is warming up to 50 DEG C, stirs 20min in the case where stirring rate is 250rpm, 1.5mol is then added
Cyclohexanone, temperature rises to 70 DEG C, stirring rate 300rpm, 30 DEG C is cooled to after persistently stirring 20min, then with 15%
Salt acid for adjusting pH value obtains mixture A to 3；
2. being put into constant pressure funnel after 5mol formaldehyde is mixed with 6mol ethyl alcohol, the temperature of mixture A is adjusted to 60
DEG C, the mixture of formaldehyde and ethyl alcohol in constant pressure funnel is added drop-wise in mixture A, is stirred when being added dropwise, rate of addition
For 2 drops/min, room temperature is naturally cooling to after stirring rate 300rpm, isothermal reaction 3.5h and obtains solution B；
3. solution B is in the case where stirring rate is 250rpm, temperature is adjusted to 45 DEG C, and the alkyl chloride of 3.0mol is added, then rises
For temperature to 87 DEG C, stirring rate is adjusted to 320rpm, constant temperature back flow reaction 3h, the reaction was continued after being then cooled to 45 DEG C 3h, is mixed
Close object C；
4. mixture C is cooled to room temperature, it is then transferred in round-bottomed flask, vacuum distillation removes solvent and excessive first
Then aldehyde places into dry 12h in vacuum oven, obtains degreaser P of the invention1。
Embodiment 2: degreaser P2And preparation method thereof
(1) degreaser P2Composition, component and molecular formula it is as follows:
Degreaser P2By 2- furylamine, formaldehyde, cyclohexanone and alkyl chloride according to molar ratio be 1:6:1.6:4 ratio react
It obtains, molecular formula is as follows:
Wherein R is C14Linear paraffin.
(2) degreaser P2The preparation method is as follows:
1. the 2- furylamine of 1mol is added in the three-necked flask that electric mixer, reflux condensing tube, thermometer are housed,
Then solvent 12mol ethyl alcohol is added, is warming up to 40 DEG C, stirs 10min in the case where stirring rate is 200rpm, 1.6mol is then added
Cyclohexanone, temperature rises to 60 DEG C, stirring rate 400rpm, 35 DEG C is cooled to after persistently stirring 25min, then with 15%
Salt acid for adjusting pH value obtains mixture A to 2；
2. be put into constant pressure funnel after 6mol formaldehyde is mixed with 7.2mol ethyl alcohol, adjust mixture A temperature to
70 DEG C, the mixture of formaldehyde and ethyl alcohol in constant pressure funnel is added drop-wise in mixture A, is stirred when being added dropwise, speed is added dropwise
Degree is 2 drops/min, is naturally cooling to room temperature after stirring rate 500rpm, isothermal reaction 4h and obtains solution B；
3. solution B is in the case where stirring rate is 300rpm, temperature is adjusted to 42 DEG C, and the alkyl chloride of 4mol is added, then heats up
To 90 DEG C, stirring rate is adjusted to 350rpm, constant temperature back flow reaction 4h, the reaction was continued after being then cooled to 40 DEG C 2h, is mixed
Object C；
4. mixture C is cooled to room temperature, it is then transferred in round-bottomed flask, vacuum distillation removes solvent and excessive first
Then aldehyde places into dry 18h in vacuum oven, obtains degreaser P of the invention2。
Embodiment 3: degreaser P3And preparation method thereof
(1) degreaser P3Composition, component and molecular formula it is as follows:
Degreaser P3It is anti-for 1:7:1.8:4.5 ratio according to molar ratio by 2- furylamine, formaldehyde, cyclohexanone and alkyl chloride
It should obtain, molecular formula is as follows:
Wherein R is C16Linear paraffin.
(2) degreaser P3The preparation method is as follows:
1. the 2- furylamine of 1mol is added in the three-necked flask that electric mixer, reflux condensing tube, thermometer are housed,
Then solvent 10mol ethyl alcohol is added, is warming up to 45 DEG C, stirs 30min in the case where stirring rate is 300rpm, 1.8mol is then added
Cyclohexanone, temperature rises to 65 DEG C, stirring rate 330rpm, 32 DEG C is cooled to after persistently stirring 30min, then with 15%
Salt acid for adjusting pH value obtains mixture A to 5；
2. be put into constant pressure funnel after 7mol formaldehyde is mixed with 8.4mol ethyl alcohol, adjust mixture A temperature to
63 DEG C, the mixture of formaldehyde and ethyl alcohol in constant pressure funnel is added drop-wise in mixture A, is stirred when being added dropwise, speed is added dropwise
Degree is 3 drops/min, is naturally cooling to room temperature after stirring rate 450rpm, isothermal reaction 3h and obtains solution B；
3. solution B is in the case where stirring rate is 200rpm, temperature is adjusted to 40 DEG C, and the alkyl chloride of 4.5mol is added, then rises
For temperature to 80 DEG C, stirring rate is adjusted to 300rpm, constant temperature back flow reaction 7h, the reaction was continued after being then cooled to 47 DEG C 1h, is mixed
Close object C；
4. mixture C is cooled to room temperature, it is then transferred in round-bottomed flask, vacuum distillation removes solvent and excessive first
Then aldehyde places into dry 16h in vacuum oven, obtains degreaser P of the invention3。
Embodiment 4: degreaser P4And preparation method thereof
(1) degreaser P4Composition, component and molecular formula it is as follows:
Degreaser P4It is reacted by 2- furylamine, formaldehyde, cyclohexanone and alkyl chloride according to molar ratio for 1:8:2:5 ratio
It arrives, molecular formula is as follows:
Wherein R is C18Linear paraffin.
(2) degreaser P4The preparation method is as follows:
1. the 2- furylamine of 1mol is added in the three-necked flask that electric mixer, reflux condensing tube, thermometer are housed,
Then solvent 13mol ethyl alcohol is added, is warming up to 48 DEG C, stirs 25min in the case where stirring rate is 220rpm, is then added 2mol's
Cyclohexanone, temperature rise to 62 DEG C, stirring rate 360rpm, persistently stir 28min after be cooled to 34 DEG C, then with 15% salt
Acid for adjusting pH value obtains mixture A to 4；
2. be put into constant pressure funnel after 8mol formaldehyde is mixed with 9.6mol ethyl alcohol, adjust mixture A temperature to
67 DEG C, the mixture of formaldehyde and ethyl alcohol in constant pressure funnel is added drop-wise in mixture A, is stirred when being added dropwise, speed is added dropwise
Degree is 3 drops/min, is naturally cooling to room temperature after stirring rate 350rpm, isothermal reaction 5h and obtains solution B；
3. solution B is in the case where stirring rate is 280rpm, temperature is adjusted to 43 DEG C, and the alkyl chloride of 5mol is added, then heats up
To 83 DEG C, stirring rate is adjusted to 400rpm, constant temperature back flow reaction 5h, the reaction was continued after being then cooled to 50 DEG C 1.5h, is mixed
Close object C；
4. mixture C is cooled to room temperature, it is then transferred in round-bottomed flask, vacuum distillation removes solvent and excessive first
Then aldehyde places into drying in vacuum oven and for 24 hours, obtains degreaser P of the invention4。
5 degreaser P of embodiment1Field application
Multi-purpose station M5Water be binary combination flooding output water, test process scale be 60m3/ d, water oil content 323mg/
L, sewage salinity 7583mg/L utilize degreaser P of the invention1To multi-purpose station M5Sewage carry out oil removal treatment, degreaser P1
Dosage be 2.4kg/d, the concentration for adding degreaser in sewage after degreaser is 40mg/L, and oil content is reduced to after processing
12.92mg/L, oil content reduce by 96.0%, reach technique requirement.
6 degreaser P of embodiment2Field application
Multi-purpose station M3Water be binary combination flooding output water, test process scale be 90m3/ d, water oil content 585mg/
L, sewage salinity 6582mg/L utilize degreaser P of the invention2To multi-purpose station M3Sewage carry out oil removal treatment, degreaser P2
Dosage be 5.85kg/d, the concentration for adding degreaser in sewage after degreaser is 65mg/L, and oil content is reduced to after processing
16.38mg/L, oil content reduce by 97.2%, reach technique requirement.
7 degreaser P of embodiment3Field application
Multi-purpose station M21Water be binary combination flooding output water, test process scale be 50m3/ d, water oil content
382mg/L, sewage salinity 9850mg/L utilize degreaser P of the invention3To multi-purpose station M21Sewage carry out oil removal treatment,
Degreaser P3Dosage be 2.0kg/d, the concentration for adding degreaser in sewage after degreaser is 40mg/L, oil content after processing
It is reduced to 7.64mg/L, oil content reduces by 98.0%, reaches technique requirement.
8 degreaser P of embodiment4Field application
Multi-purpose station M10Water be binary combination flooding output water, test process scale be 80m3/ d, water oil content
276mg/L, sewage salinity 12560mg/L utilize degreaser P of the invention4To multi-purpose station M10Sewage carry out oil removal treatment,
Degreaser P4Dosage be 2.8kg/d, the concentration for adding degreaser in sewage after degreaser is 35mg/L, oil content after processing
It is reduced to 10.5mg/L, oil content reduces by 96.2%, reaches technique requirement.
Claims (5)
1. a kind of degreaser of the binary of quaternary amine containing heterocycle combination flooding sewage, which is characterized in that its molecular formula is as follows:
Wherein, R C12~C18Straight chained alkyl.
2. a kind of degreaser of the binary of quaternary amine containing heterocycle combination flooding sewage according to claim 1, which is characterized in that institute
The R stated is C16Straight chained alkyl.
3. a kind of preparation method of the degreaser of the binary of quaternary amine containing heterocycle combination flooding sewage according to claim 1 or 2,
It is characterized in that, the preparation method specifically includes the following steps:
(1) 2- furylamine is added in the three-necked flask that electric mixer, reflux condensing tube, thermometer are housed, is then added
Etoh solvent, the additional amount of ethyl alcohol is ethyl alcohol and 2- furylamine molar ratio is 10~15:1, is warming up to 40~50 DEG C, is stirring
Rate is that 10~30min is stirred under 200~300rpm, cyclohexanone is then added, temperature rises to 60~70 DEG C, and stirring rate is
300~400rpm is cooled to 30~35 DEG C after persistently stirring 20~30min, then with 15% salt acid for adjusting pH value to 2~5,
Obtain mixture A；
(2) it is put into constant pressure funnel after mixing formaldehyde according to the molar ratio of 1:1.2 with ethyl alcohol, adjusts mixture A's
The mixture of formaldehyde and ethyl alcohol in constant pressure funnel is added drop-wise in mixture A by temperature to 60~70 DEG C, is stirred when being added dropwise
It mixes, rate of addition is 2~3 drops/min, and stirring rate is 300~500rpm, is naturally cooling to room temperature after 3~5h of isothermal reaction and obtains
To solution B；
(3) for solution B in the case where stirring rate is 200~300rpm, temperature is adjusted to 40~50 DEG C, and alkyl chloride is added, then heats up
To 80~90 DEG C, stirring rate is adjusted to 300~400rpm, and constant temperature 3~7h of back flow reaction continues after being then cooled to 40~50 DEG C
1~3h is reacted, mixture C is obtained；
(4) mixture C being cooled to room temperature, be then transferred in round-bottomed flask, vacuum distillation removes solvent and excessive formaldehyde,
Then dry 12 are placed into vacuum oven~for 24 hours, obtain degreaser.
4. a kind of preparation method of the degreaser of the binary of quaternary amine containing heterocycle combination flooding sewage according to claim 3,
Be characterized in that, the 2- furylamine, formaldehyde, cyclohexanone and alkyl chloride molar ratio be 1:5~8:1.5~2:3~5.
5. a kind of preparation method of the degreaser of the binary of quaternary amine containing heterocycle combination flooding sewage according to claim 4,
Be characterized in that, the 2- furylamine, formaldehyde, cyclohexanone and alkyl chloride molar ratio be 1:7:1.8:4.5.
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