CN101830593A - Zeolite pretreatment technology of high-concentration emulsified oil wastewater - Google Patents
Zeolite pretreatment technology of high-concentration emulsified oil wastewater Download PDFInfo
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- CN101830593A CN101830593A CN201010177898A CN201010177898A CN101830593A CN 101830593 A CN101830593 A CN 101830593A CN 201010177898 A CN201010177898 A CN 201010177898A CN 201010177898 A CN201010177898 A CN 201010177898A CN 101830593 A CN101830593 A CN 101830593A
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Abstract
The invention relates to a zeolite pretreatment technology of high-concentration emulsified oil wastewater, solving the problems that the existing treatment technology of emulsified oil wastewater has complex process, high operating cost and poor emulsified oil treatment effect, and is easy to cause secondary pollution. The technical scheme of the invention is as follows: firstly the temperature of high-concentration emulsified oil wastewater in an adjusting pool is adjusted to 0-70 DEG C, the pH value is adjusted to 0.5-2, secondly the high-concentration emulsified oil wastewater is sent to a device filled with zeolite particles, wherein the particle size of artificial zeolite is 10-50 meshes, the filling content is 2-10kg per cubic meter water and the residence time of wastewater is 0.5-2h; and finally effluent enters a post-treatment unit. The technology of the invention is simple and has low investment and operation costs, easy operations, no any chemical additive and no secondary pollution; and the oil content of the pretreated emulsified oil wastewater can be reduced to below 100mg/L and the CODCr can be lowered to below 2000mg/L, which completely meets the inflow requirements of the post-treatment biological treatment unit.
Description
Technical field
The present invention relates to a kind of waste water treatment process, the pretreated technology of employing zeolite of a kind of specifically metallurgy industry Steel Mill high-concentration emulsified oil wastewater.
Background technology
At steel industry, in order to eliminate the distortion heat that cold rolling of strip steel produces, cold rolling production uses emulsion to make lubricated or refrigerant mostly, oil in water emulsion concentration height, mainly form by the mineral oil more than the 2000mg/L or vegetables oil, emulsifying agent and water, oil in water emulsion is the milkiness shape in sewage, oil droplet size is generally 0.1～25 μ m, the electronegative hydration shell of oil droplet appearance parcel one deck, emulsification is steady state under the Action of Surfactant in water, the elaioleucite stable for extended periods of time is difficult to separate with the method for machinery.The principal feature of Steel Mill's emulsifiable oil waste water is: 1. organic content height is generally COD
Cr10000～25000mg/L; 2. complex chemical composition, main component has oiliness improver, rust-inhibiting additive, hydrotropy additive and emulsifying agent etc., 3. oily sub content height, more than 2000mg/L, if do not deal carefully with, certainly will cause severe contamination to environment, cause water body COD to raise, hydrobionts such as fish are difficult to existence and even dead.So the cold rolling of strip steel system of China Steel industry, the processing of emulsifiable oil waste water is a professional difficult problem always.
Processing to emulsifiable oil waste water at present mainly comprises physico-chemical processes, ultrafiltration membrance filter method and biological process.These three class methods respectively have shortcoming: (1) physico-chemical processes is by changing conditioned disjunction interpolation medicament emulsion to be taken off surely, thereby reaches the effect of breaking milk and removing oil, generally includes to add sour heating method and chemical agent breakdown of emulsion method.This method advantage is that reduced investment, treatment effect are good, but the assurance of process parameters is difficulty relatively, in addition, often need to add various chemical additives (as various flocculation agents) in the treating processes, can produce a large amount of chemical sludges, like this, bring new problem of environmental pollution when having caused breakdown of emulsion to deoil.(2) ultrafiltration process belongs to membrane separation process, is to rely on film and pressure to reach separating effect, and it is effective to deoil, but its shortcoming is a facility investment expense height, and operational process is safeguarded complicated, is difficult to promote the wider application.(3) utilize the biological process oil removing, because the special state of oil in water emulsion, directly use biological process to handle to exist big problem, thereby the biological process use that normally combines with additive method is as carrying out a biological disposal upon behind the chemical demulsification or after the ultrafiltration again.Cold-rolling emulsified oil reduces oil-contg and COD significantly through the physico-chemical process of front
CrAfter the concentration, have biological degradability preferably, in follow-up anaerobism or aerobic treatment, organism wherein can effectively be utilized by the biological activity bacterial classification, realizes the further reduction and the standard wastewater discharge of pollutent.Physical chemistry-biophase bonded method is maximum a kind of emulsion treatment process of domestic usefulness at present, but as previously mentioned, has serious secondary pollution problem equally as the physico-chemical processes of pretreatment technology.
Therefore the processing of emulsifiable oil waste water is the problem that experts and scholars study always, and and for example " environment protection " 1996 02 phases disclose and introduced the adsorption treatment of use natural zeolite replacement activated carbon to lower concentration oily(waste)water (oil content is less than 2%) in the paper that is called " pre-test of zeolite oil removing performance ".It is to adopt vesicular structure and the bigger serface feature of utilizing natural zeolite, utilize absorption principle that the lower concentration oily substance in the waste water is adsorbed removal, there is following problem in this oil removing mode: 1, because be when utilizing absorption principle to remove the emulsifiable oil waste water of lower concentration, because the loading capacity of zeolite is limited, then must change zeolite immediately after saturated, regular lot is changed the increase that zeolite can cause running cost, the discarded zeolite that changes can form stores, its post-processed or regeneration are again technical barriers, cause the processing cost height.2, for aforesaid high-concentration emulsified oil wastewater, if it is saturated to adopt the absorption principle processing then will soon reach absorption, deoiling effect is poor, when a large amount of high-concentration emulsified oil wastewater of actual treatment, be difficult to carry out, therefore the zeolite treatment emulsifiable oil waste water only is in theoretical analysis and laboratory stage at present, is difficult to practical application.
Summary of the invention
To the objective of the invention is in order solving the problems of the technologies described above, to provide that a kind of technology is simple, investment and running cost is low, simple to operate, oil removal efficiency is high, the Zeolite pretreatment technology of the high-concentration emulsified oil wastewater of safety and non-secondary pollution.
Technical solution of the present invention comprises that elder generation arrives 0-70 ℃ with the high-concentration emulsified oil wastewater temperature regulation in the equalizing tank, and pH sends into emulsifiable oil waste water then and is filled with artificial zeolite's particulate device to 0.5-2, and artificial zeolite's particle diameter is the 10-50 order, and loading level is 2-10kg/m
3Water, retention time of sewage are 0.5-2 hour, and last water outlet enters the subsequent disposal unit.
Described adjusting high-concentration emulsified oil wastewater temperature is to regulate by feed steam-heated method in equalizing tank, and the pH value is to regulate by the method that adds the vitriol oil, and the vitriol oil can alleviate the corrosive nature to follow-up equipment.
Described artificial zeolite's particle diameter is the 30-50 order, and the amount of filling a vacancy is 5-10kg/m
3Water, the emulsifiable oil waste water residence time is 0.5-2 hour.
Acid waste water behind the breaking milk and removing oil adds alkali adjusting pH and further removes organic pollutant to coagulating sedimentation takes place between the 6-9 automatically, and water outlet enters the subsequent disposal unit more then.Described pH value is regulated and can be selected as required, preferably adopts sodium hydroxide to regulate the pH value.
Described subsequent disposal unit is a biological processing unit.
Artificial zeolite in the described artificial zeolite's of being filled with particle device is because of after handling high-concentration emulsified oil wastewater and being partially consumed, can by additional artificial zeolite's particle in device with assurance device in artificial zeolite's loading level requirement.
Zeolite of the present invention is preferably the artificial zeolite owing to need to have certain dissolubility under acidic conditions, and the artificial zeolite is that flyash and aqueous sodium hydroxide solution obtain material at 95 ℃ of following priming reactions, can buy on market.
High-concentration emulsified oil wastewater of the present invention is meant the emulsion liquid of oil and tensio-active agent coexistence formation, and oil-contg even reaches more than the 5000mg/L COD more than 2000mg/L
CrConcentration even can be up to 1,000,000 mg/L more than 10000mg/L.
Described artificial zeolite's particulate device that is filled with can be the device of tank or canned structure, can be used for filling the artificial zeolite and feeds emulsifiable oil waste water.
The contriver after years of research and found that the inorganic mineral in artificial zeolite's material can be dissolved out under low pH condition, in the presence of the porous material artificial zeolite with high-concentration emulsified oil wastewater in tensio-active agent and oily substance react, thereby make it take off the effect that surely reaches breakdown of emulsion, it is effective to utilize this principle to handle high-concentration emulsified oil wastewater.
Further, when the acid waste water of handling through the artificial zeolite requires to regulate PH to 6-9 for satisfying water outlet,, further remove organism and oil content, particularly COD because coagulating sedimentation can take place automatically in the variation of its acidic conditions
CrContent.
Beneficial effect:
1, pretreatment technology effect of demulsification and oil removal of the present invention is good, is specially adapted to handle high-concentration emulsified oil, and the oil-contg of the emulsifiable oil waste water after the processing can drop to below the 100mg/L, COD
CrBe reduced to below the 2000mg/L, can satisfy the unitary water inlet requirement of subsequent biological treatment fully, effectively guarantee the qualified discharge of final high-concentration emulsified oil wastewater, significant aspect energy-saving and emission-reduction that promote enterprise and Sustainable development.
2, processing unit of the present invention is very simple, the zeolite raw material is easy to get, easy and simple to handle, to compare with the ultrafiltration oil removing process that present cold rolling mill generally adopts, cost of investment and running cost can reduce about 2/3rds, need not to add any chemical additive, environment is not caused any secondary pollution.
3, the present invention has changed the usual understanding of present zeolite oil removing, it is not the suction principle of utilizing zeolite, but discovered the consumption principle of zeolite, tensio-active agent and oily substance that the artificial zeolite is partly dissolved in back and the high-concentration emulsified oil wastewater react, to consume artificial zeolite's principle oil removing, therefore only need the zeolite of supplement consumed, and need not often to change zeolite, time saving and energy saving, easy and simple to handle, can there be the post-processed problem of adsorbing saturated back zeolite yet, further significantly reduced operation and maintenance cost.
4, the inventive method is specially adapted to handle the high-concentration emulsified oil wastewater from Steel Mill, for oil-containing and COD
CrHigh other industry such as machinery industry cutting fluid oil in water emulsion and medical emulsifying liquid waste water are suitable for too.
Specific embodiment
Be example with emulsion below from Steel Mill and liquid medicine injection, the further concrete the invention process method of setting forth.
Embodiment 1:
Cold-rolling emulsion waste water is sent into equalizing tank, feed steam and adjust the temperature to 60 ℃, adding vitriol oil adjusting pH is 1, and (artificial zeolite's particle diameter is 30 orders, and loading level is 5kg/m then cold-rolling emulsion to be sent into artificial zeolite's jar
3Water), intermittently stir and continue reaction after 1 hour, tangible demulsifying phenomenon occurs, a large amount of scum silica frost appear in the waste water top layer, and the water body state is converted into limpid clear state by initial oyster white emulsification attitude.Continuation adds sodium hydroxide and regulates pH to 7-8 in the acidity of skim oil slick is useless, occur tangible flocculation sediment immediately, and water quality condition is clearly better, and reaction finishes the after-filtration water outlet.Monitoring result shows, initial oil content and COD in the emulsifiable oil waste water
CrConcentration is respectively 5010mg/L and 56000mg/L, is reduced to 48mg/L and 1340mg/L after the pre-treatment respectively, satisfies the unitary water inlet requirement of subsequent biological treatment fully.After system moves for some time,, satisfy the filling requirement of zeolite by in artificial zeolite's jar, adding artificial zeolite's material to replenish the artificial zeolite who is disappeared and by consumption.
Embodiment 2, and just initial pH is that 7 medical injection emulsifying liquid waste waters are sent into equalizing tank, 0-70 ℃ of control emulsifying liquid waste water temperature, and adding vitriol oil adjusting pH is 0.5-2, (artificial zeolite's particle diameter is the 10-50 order, and loading level is 2-10kg/m to send into artificial zeolite's jar
3Water), intermittently stir and continue reaction after 0.5-2 hour, tangible demulsifying phenomenon appears, a large amount of scum silica frost appear in the waste water top layer, the water body state is converted into limpid clear state by initial oyster white emulsification attitude, adds sodium hydroxide then and regulates pH to 6-9, occurs tangible flocculation sediment immediately, water quality condition is clearly better, and reaction finishes the after-filtration water outlet.Monitoring result shows, waste water COD
Cr1000mg/L and 30mg/L have been reduced to oil concentration by 50000mg/L and 5000mg/L.
The comparative example 1: will the initial pH identical with embodiment 2 be that 7 medical injection emulsifying liquid waste water is sent into equalizing tank, 0-70 ℃ of control emulsifying liquid waste water temperature, do not regulate pH, (artificial zeolite's particle diameter is the 10-50 order, and loading level is 2-10kg/m to send into artificial zeolite's jar
3Water), intermittently stir and continue reaction after 0.5-2 hour, do not observe any demulsifying phenomenon, monitoring result shows, waste water COD
CrConcentration still about 50000mg/L, illustrates that simple zeolite adsorption can not produce treatment effect to high-concentration emulsified liquid.
The comparative example 2: just identical with embodiment 2 medical injection emulsifying liquid waste water is sent into equalizing tank, 0-70 ℃ of control emulsifying liquid waste water temperature, adding vitriol oil adjusting pH is 0.5-2, but do not mix with zeolite, intermittently stir and continue reaction after 0.5-2 hour, do not observe any demulsifying phenomenon, monitoring result shows, waste water COD
CrConcentration still about 50000mg/L, illustrates that simply adding the acid heating does not have treatment effect substantially to high-concentration emulsified liquid.
Claims (7)
1. the Zeolite pretreatment technology of a high-concentration emulsified oil wastewater, it is characterized in that, comprise earlier the high-concentration emulsified oil wastewater temperature regulation in the equalizing tank is arrived 0-70 ℃, pH is to 0.5-2, then high-concentration emulsified oil wastewater is sent into the device that is filled with zeolite granular, artificial zeolite's particle diameter is the 10-50 order, and loading level is 2-10kg/m
3Water, retention time of sewage are 0.5-2 hour, and last water outlet enters the subsequent disposal unit.
2. the Zeolite pretreatment technology of high-concentration emulsified oil wastewater as claimed in claim 1 is characterized in that, described zeolite is the artificial zeolite.
3. the Zeolite pretreatment technology of high-concentration emulsified oil wastewater as claimed in claim 1, it is characterized in that, described adjusting high-concentration emulsified oil wastewater temperature is to regulate by feed steam-heated method in equalizing tank, and the pH value is to regulate by the method that adds the vitriol oil.
4. as the Zeolite pretreatment technology of claim 1 or 2 or 3 described high-concentration emulsified oil wastewaters, it is characterized in that described zeolite particle diameter is the 30-50 order, the amount of filling a vacancy is 5-10kg/m
3Water, retention time of sewage are 0.5-2 hour.
5. as the Zeolite pretreatment technology of claim 1 or 2 or 3 described high-concentration emulsified oil wastewaters, it is characterized in that, regulate pH to coagulating sedimentation takes place between the 6-9 automatically through the acid waste water after the zeolite oil removing, further remove organism, and then enter the subsequent disposal unit.
6. as the Zeolite pretreatment technology of claim 1 or 4 described high-concentration emulsified oil wastewaters, it is characterized in that described subsequent disposal unit is a biological processing unit.
7. as the Zeolite pretreatment technology of claim 1 or 2 or 3 described high-concentration emulsified oil wastewaters, it is characterized in that, describedly be filled with zeolite in the zeolite granular device because of after handling high-concentration emulsified oil wastewater and being partly dissolved consumption, can by additional zeolite granular in device with assurance device in the loading level requirement of zeolite.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107055936A (en) * | 2017-01-03 | 2017-08-18 | 浙江新化化工股份有限公司 | A kind of preprocess method of high consistency perfume wastewater |
| CN111434621A (en) * | 2019-01-11 | 2020-07-21 | 油服环境科技(广州)有限公司 | Composite medicament for rapidly treating concentrated solution of emulsified oil wastewater |
| CN115259536A (en) * | 2022-09-09 | 2022-11-01 | 云南曲靖呈钢钢铁（集团）有限公司 | Efficient wastewater treatment system and process for steel rolling production line |
-
2010
- 2010-05-14 CN CN2010101778981A patent/CN101830593B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107055936A (en) * | 2017-01-03 | 2017-08-18 | 浙江新化化工股份有限公司 | A kind of preprocess method of high consistency perfume wastewater |
| CN111434621A (en) * | 2019-01-11 | 2020-07-21 | 油服环境科技(广州)有限公司 | Composite medicament for rapidly treating concentrated solution of emulsified oil wastewater |
| CN115259536A (en) * | 2022-09-09 | 2022-11-01 | 云南曲靖呈钢钢铁（集团）有限公司 | Efficient wastewater treatment system and process for steel rolling production line |
| CN115259536B (en) * | 2022-09-09 | 2024-06-11 | 云南曲靖呈钢钢铁（集团）有限公司 | High-efficiency wastewater treatment system and technology for steel rolling production line |
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| CN101830593B (en) | 2012-07-04 |
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