CN106395932A - Temperature-resisting and salt-resisting three-compound combination flooding produced water degreaser and preparation method thereof - Google Patents
Temperature-resisting and salt-resisting three-compound combination flooding produced water degreaser and preparation method thereof Download PDFInfo
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- CN106395932A CN106395932A CN201610983358.XA CN201610983358A CN106395932A CN 106395932 A CN106395932 A CN 106395932A CN 201610983358 A CN201610983358 A CN 201610983358A CN 106395932 A CN106395932 A CN 106395932A
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- 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
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/04—Surfactants, used as part of a formulation or alone
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention belongs to the technical field of oilfield sewage disposal, and particularly relates to a temperature-resisting and salt-resisting three-compound combination flooding produced water degreaser and a preparation method thereof. The degreaser is formed by compounding adamantine mono-quaternaries cationic surface active agent, peregal, dimethyl oleylamine sodium oxide, oleic diethanolamide and water, wherein the adamantine mono-quaternaries cationic surface active agent is a molecule having long-carbon chain alkyl non-polar group and adamantyl polar group. The degreaser is featured by simple preparation process, low cost, strong temperature resistance and salt resistance and good oil removing effect; the temperature resistance can reach 230 DEG C, the mineralization resistance can reach 230000 mg/L, and the oil removal rate can reach over 97%, which is improved by over 50% in comparison to the existed drug. Therefore, the invention can be widely applied to the oil removal technique of three-compound combination flooding produced water.
Description
Technical field
The present invention relates to a kind of degreaser for disposing polluted water in oil is and in particular to a kind of tri compound of heat-resistant salt-resistant
Drive water exit degreaser and preparation method thereof.
Background technology
With the continuous exploitation in oil field, oil recovery technique constantly develops, and successively experienced once, secondary, tertiary oil recovery, China
Part oil field has entered tertiary phase successively.Common tertiary oil recovery method have polymer displacement of reservoir oil, ternary composite oil-displacing,
Binary displacement oil (alkali-polymer displacement of reservoir oil, i.e. the AP displacement of reservoir oil), alkali drive oil, foam compsoite oil drive etc., wherein again with alkaline surfactant polymer flooding oil-field
Technology is the most typical.Relevant research shows, ternary composite driving can significantly improve oil recovery factor, before having wide application
Scape.But due to containing substantial amounts of polyacrylamide, surfactant and alkali in ternary composite flooding water extraction so that ternary composite driving
Recovered water is different from general oil-polluted water, is mainly characterized by：Sewage quantity is big, and sewage viscosity is high, and in water, oil droplet and solid suspend
The emulsion stability of thing is strong.If arbitrarily discharging these oil-polluted waters, necessarily bringing serious consequence, not only wasting water and former
Oil, and can severe contamination surrounding environment it is therefore necessary to reasonable process and utilize, to create good environmental benefit and social warp
Ji benefit.At present, the main process approach of alkaline surfactant polymer flooding oil-field sewage typically has three kinds：(1) after process reaches discharge standard
Outer row；(2) process is used as reinjected water or the useless stratum of injection of water flooding recovery after reaching certain standard；(3) drive solution as polymerization
Preparation water.From the point of view of the handling process of current oil field at home, have an economic benefit most and effective remaining reaches one
Reinjected water as water flooding recovery or the useless stratum of injection after calibration standard.But no matter which approach is it would be highly desirable to the problem solving is oil
Removal.
The deoiling method of ternary combination flooding extraction sewage mainly has chemical demulsification method, Bubble-floating Method, electrochemical process and absorption method.
(1) chemical demulsification method is by adding chemical agent in oil-polluted water, can form positively charged micelle after medicament hydrolysis, and
With negatively charged oil emulsion, charge neutrality effect can occur, reduce oil droplet surface potential, then process through other, so that oil droplet is gathered
Collection, particle diameter becomes big, thus reaching the purpose of water-oil separating；(2) Bubble-floating Method be passed through air in water or other gas produce micro-
Thin bubble, dependence bubble surface can adsorb oil droplet or the characteristic of suspension reaches detached purpose.According to bubble formation mechanism, can
To be divided into dissolved air flotation, to dissipate gas Bubble-floating Method and electrolytic gas float glass process Bubble-floating Method, wherein the bubble of dissolved air flotation generation is straight
Footpath is 20～60 μm or less, and dense uniform, best to oil emulsion treatment effect；(3) electrochemical process include electrocoagulation and
Electric spark method.Electrocoagulation is using dissolubility electrolysis oil-polluted water, goes out metal ion, metal from dissolubility anodic solution
Ion hydrolysis generates hydroxide, absorption and cohesion oil emulsion and dissolved oil, is then passed through precipitation and removes oil；Electric spark method is
Remove the oil emulsion in oil-polluted water and dissolved oil using alternating current, can produce between the conductive particle in cylinder under electric field action
Electric spark, oxidized and combustion decomposition in the presence of oil equally distributed oxygen in electric spark and water；(4) absorption method is to utilize
Adsorbing the oil in water, to the treatment effect of dissolved oil preferably, absorption method can be divided into adsorption method, ion to lipophile material
Exchange adsorption method and exclusive absorption method.Modal adsorbent is activated carbon, has good absorption property to oil, but high cost,
Regeneration is difficult, is normally only used for the advanced treating of oil-polluted water.
" synthesis of adamantane mono-quaternaries cationic surfactant " literary composition of Cai Lu is mentioned one kind and is had rigidity more by force
The adamantane surfactant of structure, this surfactant has physiologically active, good compatibility and the other functions of uniqueness
Properties such as (as antibacterial, anticorrosive, antistatic).Because the whole ring system of adamantane has straight symmetrical, high stability structure spy
Levy it is possible to occur chemisorption to form bridging with the polar substances of oil droplet, coalescent deoiling, meanwhile, live in this surface
Property agent can also effectively improve the demulsification of WO emulsion, is suitable for the oil removal treatment of ternary composite flooding water extraction.
Content of the invention
The present invention be directed to the deficiencies in the prior art and provide a kind of heat-resistant salt-resistant ternary composite flooding water extraction degreaser and
Its preparation method, the degreaser of the present invention has preparation process is simple, low cost, and heat-resistant salt-resistant performance is strong and deoiling effect is good
Feature, heatproof reaches 230 DEG C, and resistance to salinity reaches 230000mg/L, and oil removal rate reaches more than 97%, and more existing medicament improves 50%
More than.
The invention discloses a kind of ternary combination flooding extraction sewage degreaser of resisting high temperature, high salt, described degreaser is by gold
Just alkane mono-quaternaries cationic surfactant, peregal, dimethyl oil base amine sodium oxide molybdena, oleic acid diethyl amide and water compound
Form.Described adamantane mono-quaternaries cationic surfactant is that one kind has Long carbon chain alkyl non-polar group and Buddha's warrior attendant
The molecule of alkyl polar group, its molecular formula is as follows：
The component of each composition of described degreaser is as follows：
Preferably, the component of each composition of described degreaser is as follows：
Further object is that a kind of ternary combination flooding extraction sewage degreaser of resisting high temperature, high salt is provided
Preparation method, the preparation method of this degreaser specifically includes following steps：
(1) the adamantane mono-quaternaries cationic surfactant of aforementioned proportion and peregal mixing are placed into the first burning
In cup, 1/3rd of the water of addition aforementioned proportion, heat while stirring, stir speed (S.S.) is 200～300ppm, heating-up temperature is
50～60 DEG C, the heat time is 20～30min, the heat time terminate after be naturally cooling to room temperature and obtain mixed solution A；
(2) the dimethyl oil base amine sodium oxide molybdena of aforementioned proportion and oleic acid diethyl amide mixing are put in the second beaker,
/ 3rd of the water of addition aforementioned proportion, heat while stirring, and stir speed (S.S.) is 500～600ppm, heating-up temperature 30～40
DEG C, the heat time is 10～20min, the heat time terminate after be naturally cooling to room temperature and obtain mixed solution B；
(3) above-mentioned mixed solution A is poured slowly in mixed solution B, 1/3rd of the water of addition aforementioned proportion, while stirring
Mix side heating, stir speed (S.S.) is 350～450rpm, heating-up temperature is 60～70 DEG C, and the heat time is 30～50min, during heating
Between terminate after be naturally cooling to the degreaser that room temperature obtains the present invention.
A kind of degreaser of ternary composite flooding water extraction, it uses technical process as follows：
According to oil-containing situation in ternary compound oil drive output sewage, add the degreaser of the present invention in sewage, realize
Breakdown of emulsion and water-oil separating, after reclaiming petroleum substance, are processed further for subsequent technique.The concrete addition of degreaser is as follows：
(1), during oil-containing α >=500mg/L, adding degreaser to make the mass concentration of degreaser in sewage is 50～150mg/L；
During (2) 500 ＞ oil-containing α >=300mg/L, add degreaser make degreaser in sewage mass concentration be 30～
50mg/L；
During (3) 300 ＞ oil-containing α >=100mg/L, add degreaser make degreaser in sewage mass concentration be 10～
30mg/L；
(4), during oil-containing α ＜ 100mg/L, adding degreaser to make the mass concentration of degreaser in sewage is 0.5～10mg/L.
The ternary combination flooding extraction sewage degreaser that the present invention provides, it belongs to cationic surfactant, described gold
Just alkane mono-quaternaries cationic surfactant carries a positive charge, can be with the polyacrylamide anionic polymer of residual
There is electrical neutralization reaction, destroy the strong emulsifying capacity of polymer, thus playing the effect of breakdown of emulsion, simultaneously because gold on molecule
Just the extremely strong rigidity of alkane is so that the heat resistance of this molecule is very superior；Additionally, this surfactant also has stronger absorption
Performance, has stronger interface modification function；Described peregal is AEO, has good wettability
And penetrating power, there is excellent synergistic function.Dimethyl oil base amine sodium oxide molybdena and oleic acid diethyl amide have emulsification
The effect of flocculation and compatibility, can be emulsified by greasy dirt and coalesce, and play the effect of flocculation.
The present invention compared with prior art has the advantage that and beneficial effect：
(1) extensively, synthesis technique is simple, and consumption is few, and product is easily obtained and transports for the raw material sources of the degreaser of the present invention
Defeated preservation；
(2) degreaser of the present invention has stronger temperature-resistant anti-salt performance, heatproof can reach 230 DEG C, resistance to salinity reaches
230000mg/L.
(3) degreaser of the present invention has the characteristics that oil removal efficiency is high, and the oil removal rate of ternary combination flooding extraction sewage reaches
More than 97%, more existing medicament improves more than 50%, meets the requirement of the oil removing pretreatment of ternary combination flooding extraction sewage.
Specific embodiment
With reference to specific embodiment, and with reference to data, the present invention is described in further detail.It should be understood that these embodiments
The present invention solely for the purpose of illustration, rather than limit the scope of the present invention by any way.
Embodiment 1：Degreaser BE1And preparation method thereof
(1) degreaser BE1Composition and its component as follows：
According to existing document, the preparation method of described adamantane mono-quaternaries cationic surfactant is as follows：
(2) degreaser BE1Preparation method as follows：
1. 20 parts of adamantane mono-quaternaries cationic surfactant and 5 parts of peregal mixing are placed into the first beaker
In, add 30 parts of water, heat while stirring, stir speed (S.S.) is 270ppm, heating-up temperature is 50 DEG C, the heat time is 20min,
Heat time is naturally cooling to room temperature and obtains mixed solution A after terminating；
2. 8 parts of dimethyl oil base amine sodium oxide molybdena and 20 parts of oleic acid diethyl amide mixing are put in the second beaker, plus
Enter 30 parts of water, heat while stirring, stir speed (S.S.) is 500ppm, heating-up temperature is 30 DEG C, the heat time is 10min, heating
Time is naturally cooling to room temperature and obtains mixed solution B after terminating；
3. above-mentioned mixed solution A is poured slowly in mixed solution B, adds 30 parts of water, heat while stirring, speed is
350rpm, heating-up temperature is 60 DEG C, and the heat time is 30min, the heat time terminate after be naturally cooling to room temperature and obtain the present invention
Degreaser BE1.
Embodiment 2：Degreaser BE2And preparation method thereof
(1) degreaser BE2Composition and its component as follows：
According to existing document, the preparation method of described adamantane mono-quaternaries cationic surfactant is as follows：
(2) degreaser BE2Preparation method as follows：
1. 20 parts of adamantane mono-quaternaries cationic surfactant and 8 parts of peregal mixing are placed into the first beaker
In, add 40 parts of water, heat while stirring, stir speed (S.S.) is 200ppm, heating-up temperature is 53 DEG C, the heat time is 25min,
Heat time is naturally cooling to room temperature and obtains mixed solution A after terminating；
2. 15 parts of dimethyl oil base amine sodium oxide molybdena and 26 parts of oleic acid diethyl amide mixing are put in the second beaker, plus
Enter 40 parts of water, heat while stirring, stir speed (S.S.) is 530ppm, heating-up temperature is 33 DEG C, the heat time is 15min, heating
Time is naturally cooling to room temperature and obtains mixed solution B after terminating；
3. above-mentioned mixed solution A is poured slowly in mixed solution B, adds 40 parts of water, heat while stirring, stirring speed
Rate is 400rpm, and heating-up temperature is 65 DEG C, and the heat time is 50min, the heat time terminate after be naturally cooling to room temperature and obtain this
The degreaser BE of invention2.
Embodiment 3：Degreaser BE3And preparation method thereof
(1) degreaser BE3Composition and its component as follows：
According to existing document, the preparation method of described adamantane mono-quaternaries cationic surfactant is as follows：
(2) degreaser BE3Preparation method as follows：
1. 20 parts of adamantane mono-quaternaries cationic surfactant and 10 parts of peregal mixing are placed into the first burning
In cup, add 45 parts of water, heat while stirring, stir speed (S.S.) is 240ppm, heating-up temperature is 57 DEG C, the heat time is
26min, the heat time terminate after be naturally cooling to room temperature and obtain mixed solution A；
2. 18 parts of dimethyl oil base amine sodium oxide molybdena and 35 parts of oleic acid diethyl amide mixing are put in the second beaker, plus
Enter 45 parts of water, heat while stirring, stir speed (S.S.) is 550ppm, heating-up temperature is 38 DEG C, the heat time is 18min, heating
Time is naturally cooling to room temperature and obtains mixed solution B after terminating；
3. above-mentioned mixed solution A is poured slowly in mixed solution B, adds 45 parts of water, heat while stirring, stirring speed
Rate is 450rpm, and heating-up temperature is 62 DEG C, and the heat time is 35min, the heat time terminate after be naturally cooling to room temperature and obtain this
The degreaser BE of invention3.
Embodiment 4：Degreaser BE4And preparation method thereof
(1) degreaser BE4Composition and its component as follows：
According to existing document, the preparation method of described adamantane mono-quaternaries cationic surfactant is as follows：
(2) degreaser BE4Preparation method as follows：
1. 20 parts of adamantane mono-quaternaries cationic surfactant and 12 parts of peregal mixing are placed into the first burning
In cup, add 50 parts of water, heat while stirring, stir speed (S.S.) is 300ppm, heating-up temperature is 60 DEG C, the heat time is
30min, the heat time terminate after be naturally cooling to room temperature and obtain mixed solution A；
2. 20 parts of dimethyl oil base amine sodium oxide molybdena and 40 parts of oleic acid diethyl amide mixing are put in the second beaker, plus
Enter 50 parts of water, heat while stirring, stir speed (S.S.) is 600ppm, heating-up temperature is 40 DEG C, the heat time is 20min, heating
Time is naturally cooling to room temperature and obtains mixed solution B after terminating；
3. above-mentioned mixed solution A is poured slowly in mixed solution B, adds 50 parts of water, heat while stirring, stirring speed
Rate is 420rpm, and heating-up temperature is 70 DEG C, and the heat time is 45min, the heat time terminate after be naturally cooling to room temperature and obtain this
The degreaser BE of invention4.
Embodiment 5 degreaser BE1Scene application
Multi-purpose station GM2Water be ternary composite driving output water, test process scale be 100m3/ d, water oil content
935mg/L, sewage salinity 132568mg/L, carry out 65 DEG C of coolant-temperature gage, using the degreaser BE of the present invention1To multi-purpose station GM2Dirt
Water carries out oil removal treatment, degreaser BE1Dosage be 9.0kg/d, in sewage after adding degreaser, the concentration of degreaser is
90mg/L, after process, oil content is reduced to 23.4mg/L, and oil content reduces by 97.5%, reaches technological requirement.
Embodiment 6 degreaser BE2Scene application
Multi-purpose station GM5Water be ternary composite driving output water, test process scale be 80m3/ d, water oil content
756mg/L, sewage salinity 175682mg/L, carry out 62 DEG C of coolant-temperature gage, using the degreaser BE of the present invention2To multi-purpose station GM5Dirt
Water carries out oil removal treatment, degreaser BE2Dosage be 5.6kg/d, in sewage after adding degreaser, the concentration of degreaser is
70mg/L, after process, oil content is reduced to 9.8mg/L, and oil content reduces by 98.7%, reaches technological requirement.
Embodiment 7 degreaser BE3Scene application
Multi-purpose station GM15Water be ternary composite driving output water, test process scale be 60m3/ d, water oil content
876mg/L, sewage salinity 120526mg/L, water temperature 70 C, using the degreaser BE of the present invention3To multi-purpose station GM15's
Sewage carries out oil removal treatment, degreaser BE3Dosage be 4.8kg/d, in sewage after adding degreaser, the concentration of degreaser is
80mg/L, after process, oil content is reduced to 17.5mg/L, and oil content reduces by 98.0%, reaches technological requirement.
Embodiment 8 degreaser BE4Scene application
Multi-purpose station GM18Water be ternary composite driving output water, test process scale be 70m3/ d, water oil content
520mg/L, sewage salinity 168568mg/L, carry out 63 DEG C of coolant-temperature gage, using the degreaser BE of the present invention4To multi-purpose station GM18's
Sewage carries out oil removal treatment, degreaser BE4Dosage be 3.5kg/d, in sewage after adding degreaser, the concentration of degreaser is
50mg/L, after process, oil content is reduced to 14.0g/L, and oil content reduces by 97.3% and reaches technological requirement.
Claims (4)
1. a kind of ternary composite flooding water extraction degreaser of heat-resistant salt-resistant is it is characterised in that described degreaser is by adamantane list
Quaternary cationics, peregal, dimethyl oil base amine sodium oxide molybdena, oleic acid diethyl amide and water compound and form.
Described adamantane mono-quaternaries cationic surfactant is that one kind has Long carbon chain alkyl non-polar group and adamantyl
The molecule of polar group, its molecular formula is as follows：
2. the ternary composite flooding water extraction degreaser of heat-resistant salt-resistant according to claim 1 is it is characterised in that described removes
The component of each composition of finish is as follows：
3. the ternary composite flooding water extraction degreaser of heat-resistant salt-resistant according to claim 1 and 2 is it is characterised in that described
The each composition of degreaser component as follows：
4. a kind of preparation method of the ternary composite flooding water extraction degreaser of heat-resistant salt-resistant is it is characterised in that this preparation method
Specifically include following steps：
1. the adamantane mono-quaternaries cationic surfactant of aforementioned proportion and peregal mixing are placed in the first beaker,
Add aforementioned proportion water 1/3rd, heat while stirring, stir speed (S.S.) be 200～300ppm, heating-up temperature be 50～
60 DEG C, the heat time is 20～30min, the heat time terminate after be naturally cooling to room temperature and obtain mixed solution A；
2. the dimethyl oil base amine sodium oxide molybdena of aforementioned proportion and oleic acid diethyl amide mixing are put in the second beaker, in addition
State ratio water 1/3rd, heat while stirring, stir speed (S.S.) be 500～600ppm, heating-up temperature be 30～40 DEG C, plus
The hot time is 10～20min, the heat time terminate after be naturally cooling to room temperature and obtain mixed solution B；
3. above-mentioned mixed solution A is poured slowly in mixed solution B, 1/3rd of the water of addition aforementioned proportion, while stirring
Heating, stir speed (S.S.) is 350～450rpm, and heating-up temperature is 60～70 DEG C, and the heat time is 30～50min, and the heat time ties
It is naturally cooling to the degreaser that room temperature obtains the present invention after bundle.
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| CN108862502A (en) * | 2018-06-07 | 2018-11-23 | 宁波帝杨电子科技有限公司 | A kind of pulping wastewater treatment flocculant and preparation method thereof |
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