CN1067029A - A kind of breaking milk and removing oil method of oil-containing emulsifying water - Google Patents
A kind of breaking milk and removing oil method of oil-containing emulsifying water Download PDFInfo
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- CN1067029A CN1067029A CN 92104193 CN92104193A CN1067029A CN 1067029 A CN1067029 A CN 1067029A CN 92104193 CN92104193 CN 92104193 CN 92104193 A CN92104193 A CN 92104193A CN 1067029 A CN1067029 A CN 1067029A
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Abstract
The present invention relates to a kind of natural plant flocculant NCF breaking milk and removing oil method, this method is that adding coagulating agent question response is complete earlier in oil-containing emulsified water, adds natural plant flocculant NCF again.Because the organo-functional group that natural plant flocculant comprises is abundant, organic constitution is close in its structure and the oil, avidity is strong mutually, easily pass moisture film, adsorption bridging between oil droplet, thereby after adding oily(waste)water respectively with coagulating agent, can improve the breaking milk and removing oil rate greatly, also have detrimental impurity such as suspended substance, sulfide, phenols in the water of removal simultaneously.This method reagent consumption is few, so cost also reduces greatly, is suitable for the processing of the oily(waste)water of various industries.
Description
The present invention relates to a kind of treatment process of oil-containing emulsifying water, a kind of natural phant NCF and composite breaking milk and removing oil method of polymerize aluminum chloride utilized of more specifically saying so.
The waste water that petroleum refining process produces causes severe contamination to the water surrounding that the mankind depend on for existence.The principal pollutant of this waste water have oil, sulfide, phenol, acid, alkali, ammonia nitrogen, prussiate and various organism.Wherein the variation range of main contamination index is: oil 60～8000mg/l, COD100～10000mg/l, sulfide: 1～70mg/l, phenol 15～150mg/l, PH5.0～14.They are mainly from crude oil and the necessary additive of the course of processing, catalyzer and various pharmaceutical chemicals.The emulsification of the refinery water degree of depth is one of its reluctant reason, and the reason that the emulsification degree is deepened day by day is the continuous exploitation along with crude oil, and oil is complicated gradually, and contained surfactant increases in the crude oil.In addition along with the development of petroleum refining technology, the raising of working depth, auxiliary agent, the catalyst type of adding are increasing, and these have all impelled oils further to disperse, the intensification of emulsification degree, profit mixed system stability strengthens.Therefore, breakdown of emulsion more and more becomes the key that oil-containing emulsifying water is handled.
The oily(waste)water that refinery produces is one of countries in the world water surrounding primary pollution source.Processing to this class emulsified oily watewater at present remains a difficult problem that does not solve fully as yet, for this reason, has caused the concern of Chinese scholars, has explored various breaking milk and removing oil methods, with decontamination, and the protection environment.Current breaking method mainly contains two big classes: physical method and chemical process.Chemical process is to add chemical agent to react with emulsifying agent in emulsion, and the disperse phase cohesion is become greatly, thus a kind of means of carrying out oily water separation.Medicament commonly used has the agent of inorganic salt coagulation demulsification, organic polymer coargulator and compound.(1) agent of inorganic salt coagulation demulsification mainly contains aluminium salt (as PAC, BAC, AS) and molysite (as PFS, FS), their demulsification is because its hydrolysate carries out charge neutrality to elaioleucite in the water, compression double electric layer, reduce ξDian Wei, destroy the disperse phase liquid film, particle is taken off surely, thereby make oily water separation.But the throwing out that this class medicament adsorption bridging, winding volume are swept is relatively poor, and its demulsification is undesirable, can not handle degree of depth emulsive oily(waste)water.(2) organic polymer coargulator (" petrochemical complex environment protection ", 1991.NO.1.P.7～8) mainly is the polymeric flocculant polyacrylamide (PAM) of synthetic.This family macromolecule relies on wherein organo-functional group and dispersed phase drop to interact, and absorption has produced the adsorption bridging effect mutually, becomes big thereby make the dispersive oil droplet pass the moisture film cohesion, thereby makes profit separated from one another.But the synthetic polymeric flocculant costs an arm and a leg, is difficult to dissolving, demulsification is still very not outstanding.(3) compound, this is that a kind of different medicament of several chemical property is mixed as a kind of medicament by certain method used as PHM-Y(" composite macromolecular flocculant PHM-Y handles the research that contains emulsifying greasy dirt water ", Xian Institute of Highway environmental engineering institute, Luoyang Refinery, China Petrolchemical Corp., 1991.5), practice result shows, though the effect of demulsification and oil removal of compound makes moderate progress, but it is still relatively poor that it is used for the emulsifying waste water effect, and oil removal rate is 70%, and the COD clearance is 50%, and dosage is 70～100mg/l, the cost for wastewater treatment height, bad adaptability still is difficult to promote the use of.
The object of the invention provides that a kind of to have a breakdown of emulsion complete, and deoiling effect is good, the breaking milk and removing oil method that processing cost is low.
The present invention implements like this, under stirring condition, in oily(waste)water, add the aluminium salt coagulant solution for preparing in advance, after to be mixed the reacting completely, add the natural plant flocculant NCF solution for preparing in advance again, after thorough mixing reaction, the oil in the waste water, organism and other pollutents can become the flco come-up very soon or sink and be removed.
NCF is a kind of material that is processed by the polymer natural phant, it has throwing out, but it is different with the polymeric flocculant (as the PAM class) of synthetic, the kind analogy synthetic of the organo-functional group that wherein comprises many, these functional groups have comprised carboxyl, carbonyl, hydroxyl, sulfonic group, xanthan acid group etc., and especially some oil loving functional groups are that PAM is unexistent.The range of molecular weight distributions (10 of NCF
3～10
5) also wide than PAM class.These characteristics have determined that the NCF flocculation agent has stronger breaking milk and removing oil ability than synthetic class.NCF is than the easier dissolving of PAM in addition, uses more conveniently, and price is also cheap, and its price only is 1/5～1/10 of PAM, thereby easilier accepted by industry.
Aluminium salt coagulating agent since have stronger in and water-oil interface electric charge, compression double electric layer, reduction ξDian Wei, reduce the effect of the water film thickness in the emulsion, thereby produce effect of demulsification and oil removal, be used to wastewater treatment.But it is with the avidity, adsorption bridging effect of oil and to form the volume effect of sweeping of alumen ustum poor, especially in the emulsification system of You Heshui, it with oily avidity well below the natural phant series polymeric flocculant.Although aluminium salt coagulating agent can make moisture film attenuation between oil droplet, the Fan Shi reactive force strengthens, and it still can not make the dispersive tiny oil droplets pass moisture film and the phase mutual coagulation, thereby has limited the raising of oil removal efficiency, the enhancing of demulsification.After adding contains the natural plant flocculant of oil loving functional group in the oil-water emulsion system, the avidity of these high molecular organo-functional groups and oil is considerably beyond inorganic salt, it can pass moisture film, passed through charge neutrality and compressed the oil droplet of electrostatic double layer and oil droplet between adsorption bridging, tiny oil droplets is condensed rapidly become big and and water sepn, reach the purpose of breaking milk and removing oil.In addition, the alumina blossom particles that forms when the natural plant kind flocculation agent exists is big, active strong, and the volume effect of sweeping has obviously also impelled separating of flco and water.This use natural phant (NCF) is made flocculation agent and is cooperated the synergistic effect that is produced than using coagulating agent or synthetic polymeric flocculant to have unapproachable technique effect separately with aluminium salt coagulating agent.If natural macromolecule flocculating agent NCF is directly mixed composite back with coagulating agent to add in the emulsion, also can not get existing effect, because the polymeric flocculant overwhelming majority is an anionic, the coagulating agent overwhelming majority is cationic, when they directly mix, charge neutrality and various chemical reaction can take place, and drug effect is reduced, thereby reduced effect of demulsification and oil removal.And the present invention adds coagulating agent and flocculation agent separately before and after adopting, and two kinds of medicaments is played one's part to the full respectively, thereby further improve effect of demulsification and oil removal.Generally under the well-mixed situation of stirring, add coagulating agent after 1～6 minute, can add the NCF flocculation agent.
The coagulating agent that the present invention adopts mainly is an aluminum soluble salt, and polymerize aluminum chloride (PAC), aluminium chlorohydroxide (BAC), Tai-Ace S 150 (AS) are arranged.
For oleaginousness is that 6～8000mg/l, COD are that 100～10000mg/l, sulfide are that 1～70mg/l, phenol are in the waste water of 15～150mg/l, PH:5.0-14, and input NCF is that 15～25mg/l, coagulating agent are 25～50mg/l.
Breaking milk and removing oil method of the present invention has kept not only that the technical process of coagulating agent method is simple, device simple, advantage such as easy and simple to handle, and it have effect of demulsification and oil removal good, be easy to solid-liquid separation, can reduce the advantage of other pollutents such as COD in the waste water, sulfide, phenol.This method is not only applicable to oil refinery effluent and handles, and is applicable to the oily(waste)water processing of other industries such as food, machinery.
Embodiment 1:(1) gets Cangzhou Refinery 1000ml crude oil purification oily(waste)water, wherein oil-containing 2500mg/l, COD:7530mg/l;
(2) add concentration be 10% polymerize aluminum chloride (PAC) solution 0.5ml to waste water, stirred 1 minute, solution is mixed fully;
(3) the NCF aqueous solution 1ml that adds 2.5% concentration stirred 2 minutes to the aqueous solution of (2), left standstill 20 minutes, and its clear liquid is purifying waste water after the oil removing.
Get the chemical examination of purifying waste water, wherein oil-contg＜25mg/l, COD＜1882.5mg/l, oil removing rate＞99%, COD clearance＞75%.
Embodiment 2:
(1) get Cangzhou Refinery electric desalting oily(waste)water 1000ml, wherein oil-containing: 1458.3mg/l, COD:10375mg/l, temperature are 50 ℃,
(2) add concentration be 10% polymerize aluminum chloride (PAC) solution 0.6ml to waste water, stirred 1 minute, make and mix fully, react completely;
(3) the NCF solution 1ml that adds 2.5% concentration stirred 2 minutes in the solution of (2), left standstill 20 minutes, and its clear liquor is purifying waste water after the oil removing.
Get the chemical examination of purifying waste water, wherein oleaginousness＜40.1mg/l, COD＜565.9mg/l, oil removal rate＞97%, COD clearance＞94.5%.
Embodiment 3:
(1) gets the total sewer 1000ml of Cangzhou Refinery, oil-containing: 924.3mg/l wherein, COD:2441.3mg/l, sulfide: 13.1mg/l, PH:10.2;
(2) add concentration be 10% polymerize aluminum chloride (PAC) solution 0.4ml to waste water, stirs and made it to mix abundant in 1 minute, react completely;
(3) the NCF solution 1ml that adds 2.5% concentration stirred 2 minutes in the solution of (2), left standstill 20 minutes, and its clear liquor is purifying waste water after the oil removing.
Get the chemical examination of purifying waste water, wherein oil-contg＜27.1mg/l, COD:＜545.3mg/l, sulfide＜1.7mg/l, oil removing rate＞97%, COD clearance＞77.6%, sulfide clearance＞87%.
Embodiment 4:
(1) get Cangzhou Refinery electric desalting waste water and carry out dynamic experiment, flow control is 300l/h, and wherein average oleaginousness is 4784.9mg/l, COD:8732.4mg/l, sulfide: 15.14mg/l, 60 ℃ of temperature, PH:6.0～6.5;
(2) adding compound concentration in first reaction tank is 5% polymerize aluminum chloride (PAC) solution 0.24l/h, and the residence time is 6 minutes, stirs with agitator in the reaction tank to make it to mix fully, reacts completely;
(3) adding compound concentration in second reaction tank is 2.5% NCF solvent 0.24l/h, stirs with agitator in the pond solution is mixed fully, reacts completely, and solution stopped in reaction tank 5.5 minutes, entered air flotation pool,
(4) solution carries out solid-liquid separation at air flotation pool, is 1 hour in the air-float tank waterpower residence time.
Take out water sample analysis, wherein oily average content＜126.8mg/l, COD:＜1229.5mg/l, sulfide 1.63mg/l, oil removing rate＞97%, COD clearance＞85%, sulfide clearance＞89% from air flotation pool.
Embodiment 5:
(1) get the total sewer of Cangzhou Refinery and carry out dynamic experiment, flow control is 300l/h, and its water quality is: oil-contg average out to 342.56mg/l, COD:1357.88mg/l, sulfide 25.68mg/l, PH:7.6～8.0, water temperature are 35 ℃;
(2) adding concentration under agitation condition in first reaction tank is 5% polymerize aluminum chloride (PAC) solution 0.24l/h, and the first reaction tank hydraulic detention time is 6 minutes, enters second reaction tank;
(3) adding concentration under agitation condition in second reaction tank is 2.5% NCF solution 0.24l/h.The second reaction tank hydraulic detention time is 5.5 minutes, enters air flotation pool;
(4) solution carries out solid-liquid separation at air flotation pool, and the air-float tank waterpower residence time is 1 hour.
Analyze from the air flotation pool water sampling, wherein oily average content＜33.3mg/l ,/COD＜336.7mg/l, sulfide＜4.69mg/l.Oil removing rate＞90%, COD clearance＞75%, sulfide clearance＞81%.
As seen from the above-described embodiment, handle the refinery oil-containing emulsifying water with the present invention, demulsification is good, oil removing rate＞90%, COD clearance＞75%, sulfide clearance＞80%.And dosage of the present invention is few, and NCF only needs 15～25mg/l, and the PAC dosage only needs 25～50mg/l, greatly reduces processing cost.
Claims (4)
1, a kind of breaking milk and removing oil method of oil-containing emulsifying water, this method is to add the water-soluble aluminum salt coagulant in oily(waste)water, it is characterized in that coagulating agent reacts completely after, add natural plant flocculant NCF again, when adding coagulating agent and flocculation agent, solution will stir fully.
2, breaking milk and removing oil method as claimed in claim 1 is characterized in that coagulating agent is the water-soluble aluminum salt, as polymerize aluminum chloride, aluminium chlorohydroxide, Tai-Ace S 150, alum.
3, breaking milk and removing oil method as claimed in claim 1, the contamination index that it is characterized in that oily(waste)water is that oil-contg is 60～8000mg/l, COD100～10000mg/l, sulfide 1～70mg/l, phenol 15～150mg/l, PH:5.0～14 o'clock adding coagulation dosage is 25～50mg/l, NCF15～25mg/l.
4, breaking milk and removing oil method as claimed in claim 1 is characterized in that coagulating agent added oily(waste)water after 1～6 minute, added natural plant flocculant NCF again.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 92104193 CN1067029A (en) | 1992-06-10 | 1992-06-10 | A kind of breaking milk and removing oil method of oil-containing emulsifying water |
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| CN 92104193 CN1067029A (en) | 1992-06-10 | 1992-06-10 | A kind of breaking milk and removing oil method of oil-containing emulsifying water |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041621C (en) * | 1992-12-27 | 1999-01-13 | 青岛海洋大学 | Sea floating oil gelatinizer |
| CN1331767C (en) * | 2005-03-02 | 2007-08-15 | 郑州轻工业学院 | Spinning finish waste water demulsifying agent and method for preparing same |
| CN100376654C (en) * | 2003-04-23 | 2008-03-26 | 广州南沙经济技术开发区高奇环保技术有限公司 | Agglutinant for leaking oil and fabricating method |
| CN100428981C (en) * | 2006-10-26 | 2008-10-29 | 江西理工大学 | Treatment of waste emulsion |
| CN102311204A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Treatment method for wastewater generated by processing high-acid crude oil |
| CN104355435A (en) * | 2014-10-20 | 2015-02-18 | 苏州富奇诺水治理设备有限公司 | Method for treating coking wastewater |
| CN107572614A (en) * | 2017-10-23 | 2018-01-12 | 王婧宁 | Anion surfactant cleansing composition in waste water from washing wool |
| CN112441675A (en) * | 2019-08-30 | 2021-03-05 | 中国石油化工股份有限公司 | Treatment method of oily sewage and application thereof |
| CN117509987A (en) * | 2023-12-22 | 2024-02-06 | 广州中环万代环境工程有限公司 | Waste gas spraying and wastewater treatment method for setting machine |
-
1992
- 1992-06-10 CN CN 92104193 patent/CN1067029A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041621C (en) * | 1992-12-27 | 1999-01-13 | 青岛海洋大学 | Sea floating oil gelatinizer |
| CN100376654C (en) * | 2003-04-23 | 2008-03-26 | 广州南沙经济技术开发区高奇环保技术有限公司 | Agglutinant for leaking oil and fabricating method |
| CN1331767C (en) * | 2005-03-02 | 2007-08-15 | 郑州轻工业学院 | Spinning finish waste water demulsifying agent and method for preparing same |
| CN100428981C (en) * | 2006-10-26 | 2008-10-29 | 江西理工大学 | Treatment of waste emulsion |
| CN102311204A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Treatment method for wastewater generated by processing high-acid crude oil |
| CN102311204B (en) * | 2010-07-07 | 2013-08-28 | 中国石油化工股份有限公司 | Treatment method for wastewater generated by processing high-acid crude oil |
| CN104355435A (en) * | 2014-10-20 | 2015-02-18 | 苏州富奇诺水治理设备有限公司 | Method for treating coking wastewater |
| CN107572614A (en) * | 2017-10-23 | 2018-01-12 | 王婧宁 | Anion surfactant cleansing composition in waste water from washing wool |
| CN112441675A (en) * | 2019-08-30 | 2021-03-05 | 中国石油化工股份有限公司 | Treatment method of oily sewage and application thereof |
| CN117509987A (en) * | 2023-12-22 | 2024-02-06 | 广州中环万代环境工程有限公司 | Waste gas spraying and wastewater treatment method for setting machine |
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