CN105060446B - Polymer-bearing waste-water treatment organic polymer coargulator and preparation method thereof - Google Patents
Polymer-bearing waste-water treatment organic polymer coargulator and preparation method thereof Download PDFInfo
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- CN105060446B CN105060446B CN201510590969.3A CN201510590969A CN105060446B CN 105060446 B CN105060446 B CN 105060446B CN 201510590969 A CN201510590969 A CN 201510590969A CN 105060446 B CN105060446 B CN 105060446B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 22
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 15
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- 239000004411 aluminium Substances 0.000 claims abstract description 23
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 18
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims abstract description 15
- 238000010792 warming Methods 0.000 claims description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 101150103639 PB1 gene Proteins 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- -1 methyl diallyl ammonium chloride Chemical compound 0.000 claims 2
- 238000004821 distillation Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000010779 crude oil Substances 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 abstract description 2
- 230000003311 flocculating effect Effects 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
In a kind of polymer-bearing waste-water treatment organic polymer coargulator and preparation method thereof, each component is by mass fraction before hybrid reaction：Aluminium polychloride 30 40%, non-ionic polyacrylamide quality is the 5% of aluminium polychloride quality；The mass ratio 12 of PDDA and aluminium polychloride:2‑3.Weak cation type organic polymer coargulator is obtained after polymerisation, there is extremely strong flocculating effect, effective removal is containing the organic impurities and oil emulsion in poly- crude oil waste water, and the floccule quality for producing is few, form stable；The present invention is prepared using the method for compounding, and with process is simple, raw material is easy to get, and has no toxic side effect, and purifying water effect is efficiently, with low cost, the advantages of usage amount is small.
Description
Technical field
The present invention relates to the technical field of offshore oil production, specifically a kind of polymer-bearing waste-water treatment organic polymer flocculates
Agent and preparation method thereof.
Background technology
With continuing to develop for offshore petroleum industry, the polymer flooding technology of adopting starts at sea to carry out large-scale application, should
Technology can greatly improve recovery ratio, so as to obtain economic benefit higher.But, follow-up production is also given in the addition of polymer
And sewage disposal brings a series of problem, due to the presence of polyacrylamide, the oil mixing with water system of Produced Liquid there occurs
Change, the viscosity that it shows as Produced Liquid increases, and Oil in Sewage Water pearl diminishes and the ability of mutual coalescence declines between oil droplet, causes
The emulsification degree enhancing of Produced Liquid, suspended solid increases, and particle substantially attenuates, and ultimately results in polymer-bearing waste-water oil, water, suspended solid
Between separating difficulty increase, so as to increased the difficulty of Produced Liquid water-oil separating.
Sewage see it is poly- after, with sewage, polymer concentration is continuously increased, and sewage viscosity persistently increases.The flocculant for adding
Amount increases, and causes impurity siltation volume in sewerage processing equipment to increase sharply so that effectively to reduce using space.Meanwhile, it is dirty
Oil droplet ascent rate slows down in water, and oil removal efficiency reduction, causes equipment disposal ability to decline in same time.
Due to the presence of anionic polymer, the severe jamming using effect of flocculant makes flocculation be deteriorated.Contain
Suspended particulate in poly- sewage substantially attenuates, and stability enhancing, the mutual coalescence of particle and sedimentation separation are difficult, and settling character becomes
Difference.Therefore, expected flocculation is reached, it is necessary to add more medicaments, could produce flco.Substantial amounts of flocculant can make
Suspended solid is obtained to increase, and the also retention of polymer, so as to increased the load of filter plant, so as to can greatly shorten
Backwashing period, increased the workload of backwash.
By current usual used polymer-bearing waste-water inorganic agent, in application, required pharmaceutical quantities are bigger than normal, the greasy filth amount of generation
It is many, influenceed greatly, also have certain adverse effect to follow-up process and environment by site environment.
The content of the invention
The technical problem to be solved in the present invention be to provide it is specifically a kind of can effectively carry out water-oil separating containing poly- dirt
Water process organic polymer coargulator.
The present invention is adopted the technical scheme that to solve technical problem present in known technology:
Polymer-bearing waste-water treatment organic polymer coargulator of the invention, each component is by mass fraction before hybrid reaction：
Aluminium polychloride 30-40%, non-ionic polyacrylamide quality is the 5% of aluminium polychloride quality；Poly dimethyl allyl
The mass ratio 1-2 of ammonium chloride and aluminium polychloride:2-3.
The preparation method of polymer-bearing waste-water treatment organic polymer coargulator of the invention, comprises the following steps：By quality
Fraction chooses each component, wherein aluminium polychloride 30-40%, and non-ionic polyacrylamide quality is aluminium polychloride quality
5%；The mass ratio of PDDA and aluminium polychloride is in 1-2:Between 2-3；Anhydrous second is used under normal temperature
Alcohol and distilled water prepare the polymeric aluminum chlorides solution that mass percent concentration is 40%, wherein distilled water and absolute ethyl alcohol volume ratio
It is 3:1；Polymeric aluminum chlorides solution is warming up to 50 DEG C, adds non-ionic polyacrylamide, constant temperature to be sufficiently stirred for 20min, made solid
Body fully dissolves；PDDA is added dropwise, and is warming up to 65-70 DEG C, generation polymerisation, holding constant temperature, 3
It is added dropwise to complete in hour；It is warming up to 75-85 DEG C, appropriate dilute sulfuric acid is added dropwise and adjusts pH value to 3-4, maintains this temperature after 2 hours, it is cold
But to normal temperature.
The present invention can also use following technical measures：
The structural formula of described PDDA is：
The purity requirement of described non-ionic polyacrylamide is more than 99%；Alumina content in PB1 gene
It is 30%, solid content is 40% in PDDA.
The present invention has the advantages and positive effects that:
Polymer-bearing waste-water treatment organic polymer coargulator of the invention, is a kind of weak cation type organic polymer flocculation
Agent, there is extremely strong flocculating effect, effective removal containing the organic impurities and oil emulsion in poly- crude oil waste water, and produce it is cotton-shaped
Amount of substance is few, form stable；The present invention is prepared using the method for compounding, and with process is simple, raw material is easy to get, and has no toxic side effect,
Purifying water effect is efficiently, with low cost, the advantages of usage amount is small.
Specific embodiment
Referring to specific embodiment, the present invention will be described in detail.
Polymer-bearing waste-water treatment organic polymer coargulator of the invention, each component is by mass fraction before hybrid reaction：
Aluminium polychloride 30-40%, non-ionic polyacrylamide quality is the 5% of aluminium polychloride quality；Poly dimethyl allyl
The mass ratio 1-2 of ammonium chloride and aluminium polychloride:2-3.
Embodiment 1：
Each raw material components are chosen by mass percentage：Aluminium polychloride is 30%, and non-ionic polyacrylamide quality is poly-
Close the 5% of aluminium chloride quality；The mass ratio 1 of PDDA and aluminium polychloride:2；Nothing is used under normal temperature
Water-ethanol and distilled water prepare polymeric aluminum chlorides solution (distilled water and the absolute ethyl alcohol volume ratio that mass percent concentration is 40%
It is 3:1), it is put into the four-hole bottle with agitator, is warming up to 50 DEG C, adds a certain amount of non-ionic polyacrylamide；Constant temperature
Under be sufficiently stirred for 20min, fully dissolving；Reuse separatory funnel and be slowly added dropwise PDDA thereto,
And it is warming up to 65 DEG C, and there is polymerisation, control at a temperature of this, it is added dropwise to complete in 3h；80 DEG C are warming up to afterwards, are added dropwise appropriate dilute
Sulfuric acid adjusts pH value to 3, after maintaining this temperature 2h, is cooled to normal temperature and had both obtained polymer-bearing waste-water of the invention treatment with organic high
Molecular flocculant.
The assay of embodiment 1 such as table 1：Wherein
Experimental subjects：The one-level production separator water outlet of SZ36-1CEPK oil fields, OIW is more than 1000ppm.
Experimental technique：100mL experiment sewage is measured, water-bath preheating 10-15min is carried out at 72 DEG C of temperature at the scene, then
The gained flocculant of embodiment 1 of not concentration is separately added into, reel cage is put into and is uniformly rocked 60 times, water quality and suspension shape are recorded respectively
State.
The purifying water effect of the gained flocculant of embodiment 1 of the various concentrations of table 1
Embodiment 2：
Each raw material components are chosen by mass percentage：Aluminium polychloride is 35%, and non-ionic polyacrylamide quality is poly-
Close the 5% of aluminium chloride quality；The mass ratio 1 of PDDA and aluminium polychloride:3；Nothing is used under normal temperature
Water-ethanol and distilled water prepare polymeric aluminum chlorides solution (distilled water and the absolute ethyl alcohol volume ratio that mass percent concentration is 40%
It is 3:1), it is put into the four-hole bottle with agitator, is warming up to 50 DEG C, adds a certain amount of non-ionic polyacrylamide；Constant temperature
Under be sufficiently stirred for 20min, fully dissolving；Reuse separatory funnel and be slowly added dropwise PDDA thereto,
And it is warming up to 65 DEG C, and there is polymerisation, control at a temperature of this, it is added dropwise to complete in 3h；80 DEG C are warming up to afterwards, are added dropwise appropriate dilute
Sulfuric acid adjusts pH value to 3, after maintaining this temperature 2h, is cooled to normal temperature and had both obtained polymer-bearing waste-water of the invention treatment with organic high
Molecular flocculant.
The assay of embodiment 2 such as table 2：Wherein
Experimental subjects：The one-level production separator water outlet of SZ36-1CEPK oil fields, OIW is more than 1000ppm.
Experimental technique：100mL experiment sewage is measured, water-bath preheating 10-15min is carried out at 72 DEG C of temperature at the scene, then
The gained flocculant of embodiment 2 of not concentration is separately added into, reel cage is put into and is uniformly rocked 60 times, water quality and suspension shape are recorded respectively
State.
The purifying water effect of the gained flocculant of embodiment 2 of the various concentrations of table 2
Embodiment 3：
Each raw material components are chosen by mass percentage：Aluminium polychloride is 35%, and non-ionic polyacrylamide quality is poly-
Close the 5% of aluminium chloride quality；The mass ratio 2 of PDDA and aluminium polychloride:3；Nothing is used under normal temperature
Water-ethanol and distilled water prepare polymeric aluminum chlorides solution (distilled water and the absolute ethyl alcohol volume ratio that mass percent concentration is 40%
It is 3:1), it is put into the four-hole bottle with agitator, is warming up to 50 DEG C, adds a certain amount of non-ionic polyacrylamide；Constant temperature
Under be sufficiently stirred for 20min, fully dissolving；Reuse separatory funnel and be slowly added dropwise PDDA thereto,
And it is warming up to 65 DEG C, and there is polymerisation, control at a temperature of this, it is added dropwise to complete in 3h；80 DEG C are warming up to afterwards, are added dropwise appropriate dilute
Sulfuric acid adjusts pH value to 3, after maintaining this temperature 2h, is cooled to normal temperature and had both obtained polymer-bearing waste-water of the invention treatment with organic high
Molecular flocculant.
The assay of embodiment 3 such as table 3：Wherein
Experimental subjects：The one-level production separator water outlet of SZ36-1CEPK oil fields, OIW is more than 1000ppm.
Experimental technique：100mL experiment sewage is measured, water-bath preheating 10-15min is carried out at 72 DEG C of temperature at the scene, then
The gained flocculant of embodiment 3 of not concentration is separately added into, reel cage is put into and is uniformly rocked 60 times, water quality and suspension shape are recorded respectively
State.
The purifying water effect of the gained flocculant of embodiment 3 of the various concentrations of table 3
Embodiment 4：
Each raw material components are chosen by mass percentage：Aluminium polychloride is 35%, and non-ionic polyacrylamide quality is poly-
Close the 5% of aluminium chloride quality；The mass ratio 2 of PDDA and aluminium polychloride:3；Nothing is used under normal temperature
Water-ethanol and distilled water prepare polymeric aluminum chlorides solution (distilled water and the absolute ethyl alcohol volume ratio that mass percent concentration is 40%
It is 1:1), it is put into the four-hole bottle with agitator, is warming up to 50 DEG C, adds a certain amount of non-ionic polyacrylamide；Constant temperature
Under be sufficiently stirred for 20min, fully dissolving；Reuse separatory funnel and be slowly added dropwise PDDA thereto,
And it is warming up to 65 DEG C, and there is polymerisation, control at a temperature of this, it is added dropwise to complete in 3h；80 DEG C are warming up to afterwards, are added dropwise appropriate dilute
Sulfuric acid adjusts pH value to 3, after maintaining this temperature 2h, is cooled to normal temperature and had both obtained polymer-bearing waste-water of the invention treatment with organic high
Molecular flocculant.
The assay of embodiment 4 such as table 4：Wherein
Experimental subjects：The one-level production separator water outlet of SZ36-1CEPK oil fields, OIW is more than 1000ppm.
Experimental technique：100mL experiment sewage is measured, water-bath preheating 10-15min is carried out at 72 DEG C of temperature at the scene, then
The gained flocculant of embodiment 4 of not concentration is separately added into, reel cage is put into and is uniformly rocked 60 times, water quality and suspension shape are recorded respectively
State.
The purifying water effect of the gained flocculant of embodiment 4 of the various concentrations of table 4
Polymer-bearing waste-water treatment organic polymer coargulator of the invention is wadded a quilt with cotton to having flocculation rate fast containing poly- crude oil sewage
Shape thing is solid, water quality is good, the features such as consumption is few.
The above, is only presently preferred embodiments of the present invention, and any formal limitation is not made to the present invention, though
So the present invention is disclosed as above with preferred embodiment, however, the present invention is not limited to, it is any to be familiar with this professional technology people
Member, without departing from the scope of the present invention, can utilize the technology contents for disclosing to make a little change or modification certainly, into
It is the Equivalent embodiments of equivalent variations, as long as being the content without departing from technical solution of the present invention, according to technical spirit of the invention
Any simple modification, equivalent variations and the modification made to above example, belong in the range of technical solution of the present invention.
Claims (3)
1. a kind of preparation method of polymer-bearing waste-water treatment organic polymer coargulator, comprises the following steps：Selected by mass fraction
Each component, wherein aluminium polychloride 30-40% are taken, non-ionic polyacrylamide quality is the 5% of aluminium polychloride quality；Poly- two
The mass ratio of methyl diallyl ammonium chloride and aluminium polychloride is in 1-2:Between 2-3；Absolute ethyl alcohol and distillation are used under normal temperature
Water prepares the polymeric aluminum chlorides solution that mass percent concentration is 40%, and wherein distilled water and absolute ethyl alcohol volume ratio is 3:1；Will
Polymeric aluminum chlorides solution is warming up to 50 DEG C, adds non-ionic polyacrylamide, constant temperature to be sufficiently stirred for 20min, make solid fully molten
Solution；PDDA is added dropwise, and is warming up to 65-70 DEG C, generation polymerisation, holding constant temperature, drop in 3 hours
Add into；75-85 DEG C is warming up to, appropriate dilute sulfuric acid is added dropwise and is adjusted pH value to 3-4, maintain this temperature after 2 hours, be cooled to often
Temperature.
2. the preparation method of polymer-bearing waste-water treatment organic polymer coargulator according to claim 1, it is characterised in that：
The structural formula of PDDA is：
3. the preparation method of polymer-bearing waste-water treatment organic polymer coargulator according to claim 1 and 2, its feature exists
In：The purity requirement of non-ionic polyacrylamide is more than 99%；Alumina content is 30%, poly- two in PB1 gene
Solid content is 40% in methyl diallyl ammonium chloride.
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| CN105461033B (en) * | 2015-11-24 | 2018-09-18 | 朱正培 | A kind of aluminium salt reinforcing agent and preparation method thereof |
| CN105692830B (en) * | 2016-02-24 | 2018-08-24 | 中国海洋石油集团有限公司 | A kind of clear water method of polymer in shielding polymer-bearing waste-water |
| CN107790295A (en) * | 2017-09-28 | 2018-03-13 | 楚雄滇中有色金属有限责任公司 | A kind of high fineness flotation concentrates sedimentation method of Copper making clinker |
| CN109179607A (en) * | 2018-10-10 | 2019-01-11 | 湖南凯涛环保科技有限公司 | A kind of preparation method of efficient dephosphorization aluminium polychloride |
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|---|---|---|---|---|
| CN101323474A (en) * | 2007-06-13 | 2008-12-17 | 中国石油天然气股份有限公司 | Novel oilfield sewage treatment coagulant |
| CN102515333A (en) * | 2011-12-19 | 2012-06-27 | 上海久安水质稳定剂厂 | Special flocculant for oily wastewater and manufacturing method for same |
| CN103193306A (en) * | 2013-04-15 | 2013-07-10 | 安徽大地熊新材料股份有限公司 | Compound coagulant |
| CN104085970A (en) * | 2014-08-04 | 2014-10-08 | 克拉玛依市三达新技术开发有限责任公司 | Thick oil sewage treatment coagulating agent, and preparation method and application thereof |
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| US7438828B2 (en) * | 2003-12-23 | 2008-10-21 | Wing Yip Young | Water treatment mixture |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323474A (en) * | 2007-06-13 | 2008-12-17 | 中国石油天然气股份有限公司 | Novel oilfield sewage treatment coagulant |
| CN102515333A (en) * | 2011-12-19 | 2012-06-27 | 上海久安水质稳定剂厂 | Special flocculant for oily wastewater and manufacturing method for same |
| CN103193306A (en) * | 2013-04-15 | 2013-07-10 | 安徽大地熊新材料股份有限公司 | Compound coagulant |
| CN104085970A (en) * | 2014-08-04 | 2014-10-08 | 克拉玛依市三达新技术开发有限责任公司 | Thick oil sewage treatment coagulating agent, and preparation method and application thereof |
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Effective date of registration: 20231207 Address after: The three area of Qin Tai Xiang Nan 256600 Shandong province Binzhou City foreshore City Patentee after: SHENGLI OILFIELD HUABIN CHEMICAL Co.,Ltd. Address before: M2, Haitai Green Industry Base, No. 6 Haitai Development Road, Nankai District, Tianjin, 300384 Patentee before: E-TECH ENERGY TECHNOLOGY DEVELOPMENT Corp. |