CN1187273C - Method of treating oil containing waste water using anion cation mixed ion resin - Google Patents
Method of treating oil containing waste water using anion cation mixed ion resin Download PDFInfo
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- CN1187273C CN1187273C CNB03129698XA CN03129698A CN1187273C CN 1187273 C CN1187273 C CN 1187273C CN B03129698X A CNB03129698X A CN B03129698XA CN 03129698 A CN03129698 A CN 03129698A CN 1187273 C CN1187273 C CN 1187273C
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Abstract
The present invention relates to a method of treating wastewater containing oil by using anion and cation mixed ion resin. Firstly, wastewater containing oil filtered by a separation tank enters a water pump and then enters a coalesing device for the separation of oil and water. In the coalesing device, hydrophilic lipophilic charged materials, such as anion cation mixed ion resin, etc. are used as coalescing medium of emulsified oil to form an anion-cation ion resin column. The function of destroying a double electric layer of emulsified liquid and the properties of high lipophilicity and high waterwetness of the anion-cation ion resin column complete the demulsification of emulsified particles and realize the two phase separation of oil and water. The present invention realizes the efficient recovery of oil resources without the addition of any medicament, has the advantages of little environmental pollution, simple structure of a processing unit, low cost, and basically no need of maintenance care, and is suitable for treating various types of wastewater containing oil.
Description
Technical field:
The present invention relates to a kind of treatment process of oily(waste)water, relate in particular to a kind of method of negative and positive hybrid ionic plastic resin treatment oily(waste)water, under the situation of not adding any medicament, industrial oily waste water is carried out oily water separation, belong to environmental technology and technical field of chemical separation.
Background technology:
Oily(waste)water is mainly from processing, refinement, storage and the transportation of petroleum industry PetroChina Company Limited. and oil product; Emulsifiable oil waste waters such as the steel rolling water that produces in the machinofacture course of processing, cooling-lubricant; The oily(waste)water of the dischargings such as oil-washing tank of carwash, railway locomotive depot in the transportation industry; And also contain a large amount of oil in catering trade, food-processing industry, textile industry and other the manufacturing waste water.Oily(waste)water directly discharges, and the harm that causes mainly shows: on the one hand owing to the covering of pasta, completely cut off the surperficial reoxygenation of water body, make in the water body and can take place to worsen phenomenon by biochemical organism, water body has been lost self-purification capacity.The minimizing of water body dissolved oxygen has destroyed the eubiosis in the water again.And the oxygenizement of oils will increase the organic loading of water body, quicken water body and worsen.Some straight chain arene compounds have indirect or direct toxic action to organism in water in the oil, and the existence of polynuclear aromatics also can cause the raising of human cancer sickness rate, and the oil in the water can make the water quality fouling that degenerates, and influences HUMAN HEALTH; Emulsified oily watewater mainly is organic pollution to the pollution of water on the other hand, and organic content is all very high in the emulsion, and COD (chemical oxygen demand (COD)) is everlasting 1～10
2Between the g/L order of magnitude, the reason that organic content is high is not only the cause because of oil in water emulsion, and because most of emulsifying agent is a hydrocarbon-surfactant.Therefore, oily(waste)water must could discharge through after the suitable processing.So processing and recovery of oil Research on New to oily(waste)water are necessary with exploitation.
From the wastewater treatment angle, easier to the processing of oil slick, but to emulsification oil handling relative difficult.Many emulsified oily watewater treatment technologies have been developed both at home and abroad, as centrifugation, membrane filtration, flocculation, electrochemical process, chemical method, adsorption filtration method and biological process etc.Wherein chemical method (as breakdown of emulsion and flocculation) is used more, it needs to add chemical agent and carries out " breakdown of emulsion " earlier in waste water in treating processes, add flocculation agent again emulsified particle more stable in the emulsion is removed by flocculation, thereby produce a lot of flocculation mud.Do so not only and can cause secondary pollution, and the oil phase of separating can not reclaim, processing cost is also than higher.Even so, the water outlet of processing often also is difficult to reach emission standard, and this is insoluble always for many years problem.Other the whole bag of tricks also respectively have its shortcoming.Several simply methods of refiltered oil resource are to use as far as possible simply and the demulsification efficiency of the apparatus and method for of less energy-consumption raising oily(waste)water under the prerequisite of not adding any medicament at present.Though centrifuging and electrostatic demulsifying method need not added chemical agent, energy consumption height, particularly centrifuging, and treatment effect is good inadequately, coarse method energy consumption is lower, does not also need to add chemical agent, but its filler haves much room for improvement, and treatment effect has much room for improvement.
Summary of the invention:
The objective of the invention is at the deficiencies in the prior art, propose a kind of emulsified oil-containing waste water treatment process based on physical method, do not need to add any chemical additive, working cost is low, and oily resource high-efficiency is reclaimed.
For realizing such purpose, in the oily wastewater treatment method of the present invention, earlier oily(waste)water is filtered the laggard water pump of going into through oil trap, enter the coarse device again with oily water separation, after water and the oil of settling bowl after obtaining handling.Principal character of the present invention is to have adopted the coarse device in oily(waste)water is handled; and in the coarse device, fill the amphiphatic materials such as negative and positive hybrid ionic resin of certain altitude; form the zwitterion resin column; zwitterion resin column diameter is 3cm; highly be 50cm, wherein the volume ratio of resin cation (R.C.) and resin anion(R.A) is 1～2.5: 1.The feed liquor flow that enters the coarse device is 10L/H, and the feed liquor temperature is 10 ℃～60 ℃, and the operation treatment time is 1～5 hour.
The present invention uses the zwitterion resin column as a processing unit in the processing of oily(waste)water; adopt hydrophilic and oleophilic such as negative and positive hybrid ionic resin and charged material as the steady coalescing medium of taking off of oil in water emulsion; be filled in the coarse device; utilized the certain electric density of zwitterion resin; have the effect that destroys the emulsion electrostatic double layer, have height oleophylic and hydrophilic double properties simultaneously again.When oily(waste)water passes through resin column, the electrostatic double layer of various emulsification particulates and oleophylic thereof, hydrophilic balance is destroyed, thereby finished the breakdown of emulsion of emulsified particle, simultaneously oily(waste)water during by resin column again owing to have bigger avidity between the little oil droplet, so continuous inflow along with oily(waste)water, become big gradually to such an extent as to little oil droplet is constantly coalescent, and under the effect of fluidic impellent, make diameter break away from resin column than original much bigger coalescent oil droplet, thereby realize that two of oil and water is separated, promptly be issued to and handled with oil in water emulsion in the situation of not adding any medicament, disperseing wet goods is the purpose of master's oily(waste)water.Testing research shows that in the method for the present invention, water temperature is to the obvious effect of oily(waste)water treatment effect, and along with the rising of water temperature, treatment effect improves, when temperature during at 60 ℃ the water outlet oleaginousness be below the 10mg/L.Stability experiment shows simultaneously, and along with the increase of handling the water yield, stability is better always, reaches 5 hours when the treatment time, and treatment effect does not have to change substantially, maintains about 97%.
The present invention can utilize the waste and old zwitterion resin after water treatment is used that oily(waste)water is handled, and can reach satisfied effect equally, has realized the purpose of the treatment of wastes with processes of wastes against one another.
The present invention has accomplished not need to add any chemical additive, is not afraid of hot operation, based on static electric charge and materialization parent profit effect breakdown of emulsion, has realized that oily resource high-efficiency reclaims, and reduces environmental pollution; Processing unit is simple in structure, cost is low, floor space is little, do not need maintenance management substantially.The present invention is fit to various types of oily(waste)waters and handles.
Description of drawings:
Fig. 1 is oily(waste)water processing technological flow figure of the present invention.
As shown in Figure 1, oily(waste)water earlier advances oil trap through gate valve, filters the laggard water pump of going into, and then enters the coarse device by gate valve, oily water separation after the settling bowl processing again, thus reach the wastewater treatment purpose.
Fig. 2 adopts the zwitterion resin column as the coarse schematic representation of apparatus for the present invention.
Embodiment:
Below in conjunction with accompanying drawing and by specific embodiment technical scheme of the present invention is further described.
The process flow sheet of oily wastewater treatment method of the present invention as shown in Figure 1, oily(waste)water enters water pump, and then enters the zwitterion resin column by gate valve by the gate valve oil trap of flowing through, and enters settling bowl at last, promptly gets treating water and oil.Wherein the zwitterion resin column is by 1～2.5: 1 zwitterion resin is formed, and zwitterion resin column diameter is 3cm, highly is 50cm, as shown in Figure 2.Waste water is flow to from the bottom by certain flow velocity, because the zwitterion resin has affinity to oil content, and has certain density, so the dispersed substance in the oily(waste)water is held back by the zwitterion resin column, because of bigger force of cohesion is arranged between oil and the oil, so continuous injection along with oily(waste)water, the olesome diameter that the zwitterion resin column is held back increases gradually, when particle diameter increases to to a certain degree the time, just under the fluidic impellent, make diameter break away from the zwitterion resin, thereby realize the separation of profit than original much bigger oil droplet.The oily(waste)water water temperature of handling is 10～60 ℃.By the oily(waste)water that the inventive method is handled, oil removal rate can reach 97%, and then has reached the purpose of efficient processing oily(waste)water.
Embodiment 1
The feed liquor temperature is to the influence test of oily water separation.
Oily(waste)water earlier enters high-pressure pump by the gate valve oil trap of flowing through, and then enter the coarse device by gate valve, employed zwitterion resin column height is 50cm in the coarse device, diameter is 3cm, and wherein resin anion(R.A) adopts strong-basicity styrene series anion exchange resin 201 * 7 (717); Resin cation (R.C.) adopts strongly acidic styrene type cation exchange resin 001 * 7, and the zwitterion resin ratio is 1: 1.The content that enters the feed liquor oil of zwitterion resin column is 500mg/L, and the feed liquor flow is 10L/H, after settling bowl is finished oily water separation.The feed liquor temperature is respectively 20 ℃, 40 ℃, 60 ℃, and be 5 hours steady time, and corresponding fluid oil-containing is respectively 13.71mg/L, 11.05mg/L, 7.39mg/L.
Embodiment 2
Feed liquor is tested the influence of oily water separation steady time.
Oily(waste)water earlier enters high-pressure pump by the gate valve oil trap of flowing through, and then enter the coarse device by gate valve, employed zwitterion resin column height is 50cm in the coarse device, diameter is 3cm, and wherein resin anion(R.A) adopts strong-basicity styrene series anion exchange resin 201 * 7 (717); Resin cation (R.C.) adopts strongly acidic styrene type cation exchange resin 001 * 7, and the zwitterion resin ratio is 1: 1.The content that enters the feed liquor oil of zwitterion resin column is 500mg/L, and the feed liquor flow is 10L/H, and the feed liquor temperature is 10～20 ℃, after settling bowl is finished oily water separation.Be respectively working time 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, corresponding fluid oil-containing is respectively 15.6mg/L, 14.2mg/L, 14.1mg/L, 14.2mg/L, 14.2mg/L.
Can find out that by above data feed liquor all can reach satisfied treatment effect steady time in 1～5 hour scope.Handle through the operation more than 2 hours, the oily(waste)water after handling by the zwitterion resin column, the water outlet oleaginousness is basicly stable at 14.2mg/L, and oil removal rate reaches more than 96%.
Embodiment 3
Technical process and install is the samely adopted old zwitterion resin to do filler and is carried out wastewater treatment, and wherein the zwitterion resin ratio is 1: 1, water temperature is 20 ℃, and flooding velocity is 10L/H, and the water inlet oil-containing is 500mg/L, the water outlet oil-containing is 28.25mg/L, and the clearance of oil is 94.35%.Hence one can see that, adopts old zwitterion resin effect also about 95%, so can utilize waste and old zwitterion resin that oily(waste)water is handled, realized the purpose of the treatment of wastes with processes of wastes against one another.
Embodiment 4
Technical process and install the same, adopt different zwitterion resin ratio that oily(waste)water is handled, water temperature is 20 ℃, flooding velocity is 10L/H, the water inlet oil-containing is 500mg/L, the zwitterion ratio was respectively 1: 1,1: 1.5,1: 2,1: 2.5, and corresponding water outlet oil-containing is respectively 17.92mg/L, 15.18mg/L, 13.09mg/L, 14.98mg/L.
Can find out thus, zwitterion resin ratio difference, the effect of processing is also inequality, but the big more treatment effect of the ratio that resin cation (R.C.) accounts in certain scope is good more.
Claims (2)
1, a kind of method of negative and positive hybrid ionic plastic resin treatment oily(waste)water; it is characterized in that earlier oily(waste)water is filtered the laggard water pump of going into through oil trap; enter the coarse device again with oily water separation; it is 3cm that the coarse device adopts diameter; highly be the zwitterion resin column of 50cm, wherein the volume ratio of resin cation (R.C.) and resin anion(R.A) is 1～2.5: 1, and the feed liquor flow that enters the coarse device is 10L/ hour; the feed liquor temperature is 10 ℃～60 ℃, and the operation treatment time is 1～5 hour.
2, the method for negative and positive hybrid ionic plastic resin treatment oily(waste)water as claimed in claim 1, what it is characterized in that the employing of zwitterion resin is respectively strong-basicity styrene series anion exchange resin 201 * 7 and strongly acidic styrene type cation exchange resin 001 * 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03129698XA CN1187273C (en) | 2003-07-03 | 2003-07-03 | Method of treating oil containing waste water using anion cation mixed ion resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03129698XA CN1187273C (en) | 2003-07-03 | 2003-07-03 | Method of treating oil containing waste water using anion cation mixed ion resin |
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| CN1478727A CN1478727A (en) | 2004-03-03 |
| CN1187273C true CN1187273C (en) | 2005-02-02 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101164922B (en) * | 2007-09-29 | 2011-09-14 | 上海达人环保科技有限公司 | Oil-containing sewage treatment system |
| CA2708870C (en) * | 2009-08-05 | 2015-05-19 | Rohm And Haas Company | Polymers as additives for the separation of oil and water phases in emulsions and dispersions |
| CN103265130A (en) * | 2013-04-26 | 2013-08-28 | 江苏思澳环保科技有限公司 | Physical oil-water mixed liquid separator |
| WO2015017972A1 (en) * | 2013-08-06 | 2015-02-12 | Dow Global Technologies Llc | Method for treating oil-containing aqueous mixtures with cation exchange resin |
| CN107530590B (en) | 2015-03-17 | 2021-03-19 | 唐纳森公司 | Hydrocarbon-in-water purification system |
| CN107427739A (en) * | 2015-03-17 | 2017-12-01 | 唐纳森公司 | Water bag hydrocarbon purifies anion exchange system |
| CN110078161A (en) * | 2019-04-03 | 2019-08-02 | 华东理工大学 | A kind of device and method of offshore platform production waste water compact efficient oil removing |
| CN109942052A (en) * | 2019-04-10 | 2019-06-28 | 上海米素环保科技有限公司 | A kind of method and device of oil field reinjection water depth oil removing |
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