CN101168464B - Economy type treatment method and device for waste magnetic suspension liquid - Google Patents
Economy type treatment method and device for waste magnetic suspension liquid Download PDFInfo
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- CN101168464B CN101168464B CN2006101174468A CN200610117446A CN101168464B CN 101168464 B CN101168464 B CN 101168464B CN 2006101174468 A CN2006101174468 A CN 2006101174468A CN 200610117446 A CN200610117446 A CN 200610117446A CN 101168464 B CN101168464 B CN 101168464B
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Abstract
The invention discloses an economic process for treating waste magnetic suspension, and a relative device, wherein the process comprises feeding sewage, adding phosphorous removal agent, to remove phosphate radical and adjust pH to 10 around, and adding water treatment agent (the best embodiment is ULTIMER7751) with degreasing, flocculating and aggregating functions, mixes to coagulate water and drug, then separating deposition, to separate oil, sludge and clean water, and discharging independently that discharges clean water at discharge standard to a turbid circulation system to be treated and discharged, while oil and sludge are discharged from the bottom of a reactor into a sludge underground pot. The inventive device comprises a waste magnetic suspension pot, a reactor, and a sludge underground pot, wherein the reactor and the waste magnetic suspension pot, the reactor and the sludge underground pot are respectively arranged with a pump between to connect the pipeline of a valve. The invention has the advantages of low cost, simple application, non-limitation by site condition, and high handling capacity or the like.
Description
Technical field
The invention belongs to the technology for treating industrial waste water field, relate to the purification techniques of employed waste magnetic suspending liquid in the steel tube flaw detection process, be specifically related to a kind of economical treatment process and device thereof of waste magnetic suspending liquid.
Background technology
Employed magnetic flaw detection ink in steel tube flaw detection, its main component are that fluorescent material and dispersion agent mix by a certain percentage, and fluorescent material wherein is to coat one deck fluorochrome with magnetic powder to make.It mainly is suspended substance, oil content, chemical oxygen demand (COD), phosphate radical etc. that the waste magnetic suspending liquid composition is explained with water-quality guideline.During actual the flaw detection, magnetic flaw detection ink generally is repeatedly and uses, even but in producing sometimes fluorochrome come off and still can not change magnetic flaw detection ink, and just increase magnetic, and causing working-surface all is magnetic, contrast degenerates and causes omission, therefore, in order to guarantee the quality of detecting a flaw, must in time change magnetic flaw detection ink, so will produce a large amount of waste magnetic suspending liquids.
From Baosteel environmental monitoring station certain analytical data, pH 8.0, suspended substance 2320mg/L, oil content 1530mg/L, chemical oxygen demand (COD) 14200mg/L, phosphate radical 126mg/L, ammonia nitrogen 85mg/L to the waste magnetic suspending liquid composition.The environmental pollutant of high density like this are because so its singularity can not find suitable treatment process, for a long time the discharging of can only limiting the quantity of.Along with the high speed development of industry, the contradiction of waste water treatment is more and more outstanding, must be by control water quality to reach the purpose of water saving and protection environment.Therefore, waste magnetic suspending liquid could discharge after need reaching certain requirement through processing.
For the discharging of waste magnetic suspending liquid, the research of this respect both at home and abroad is a lot, and focus is how to guarantee to make crucial controlling index such as suspension content, oil content, chemical oxygen demand (COD), phosphate radical to reach requirement.
At present, the processing of waste magnetic suspending liquid has two kinds of technology:
1, first kind is in conjunction with the on-the-spot turbid recycle system, simple oxidation iron sheet filtering technique.
Its method is: waste magnetic suspending liquid is directly entered in the iron scale hole, directly get back to the turbid recycle system after filtering through the simple oxidation iron sheet.Through the waste liquid that this method is handled, clearances such as its phosphate radical, oil, organism are very little, directly return the turbid recycle system water quality of the turbid recycle system has been caused great negative impact, bring hidden danger to production, have the risk of contaminate environment.In addition, this waste magnetic suspending liquid is directly entered the iron scale stockyard, remove the way of the various impurity of waste magnetic suspending liquid middle and high concentration by the simple filtration of iron scale, because it is still very poor that it filters the back effluent quality, make impurity such as a large amount of oil contents, suspended substance directly enter the turbid recycle system, this has increased the load of the turbid recycle system to a great extent, causes strainer knot plate to lose efficacy easily, there is very big hidden danger, therefore can only limits the amount of entering of waste magnetic suspending liquid.
2, second kind is " the pre-membrane filtration treatment technology of sorbent material ".
See Fig. 2, described technology comprises the technological process of following order: coagulation, pre-film filters and back flushing.
The characteristics of this technology are the sorbent material pre-coating films, are similar to packed bed filtering technique and ultrafiltration membrance filter technology.At first adsorbent fines is coated in the filter element surface in advance, and then with sewage by scribbling the filter element of sorbent material in advance, make the sewage processing that is purified.Along with sewage passing through on filter element, the pressure difference of filter element both sides after pressure reduction is increased to certain numerical value, is cut off sewage in continuous increase, carries out back flushing, and the sorbent material that is coated in advance on the filter element then can come off automatically.The difficult point of this technology maximum is that precision is too high, and membrane filtration technique has strict requirement for the water quality that enters, and all kinds of impurity concentrations of waste magnetic suspending liquid are all very high, must cause filtering premature failure, and it is also very difficult to regenerate.Be used for the laboratory still can, can't apply to the processing of extensive waste magnetic suspending liquid for a long time continuously.
Baosteel company in 2002 once taked the pre-membrane filtration technique of sorbent material (patent No. CN1565996) that waste magnetic suspending liquid is handled and did experiment, to need to increase facility investment in the reality bigger but this technology is because of using, and a series of working costs such as routine maintenance, spare parts consumption are also very high, add factors such as sorbent material is difficult for buying and fail to obtain to promote.
Large-scale steel pipe factory has 400 tons waste magnetic suspending liquid to handle every year approximately, therefore, in order to reduce system burden, guarantee that the water treatment system discharge of wastewater is up to standard, must find a kind of on-the-spot utilization of enterprise that is suitable for as early as possible, can be extensive, low-cost, the short-cut method of handling waste magnetic suspending liquid well.
Summary of the invention
The technical problem to be solved in the present invention is: a kind of cost is low, simple and easy to do, be not subjected to the waste magnetic suspending liquid that field condition restricts, the batch processed amount is big economical treatment process and device thereof are provided.
Technical scheme of the present invention is as follows:
The economical treatment process of a kind of waste magnetic suspending liquid, it comprises the following steps:
1) sewage flows into: with the waste magnetic suspending liquid injecting reactor;
2) dephosphorization: add dephosphorization agent, remove phosphate radical, regulate about PH to 10, make positive phosphorus≤1ppm;
3) coagulating: add water treatment agent, stir, medicament and water are fully reacted with oil removing, flocculation, cohesion;
4) precipitate and separate: stop to stir, mixed solution is remained static, precipitation is separated oil content, mud and clear water, clear water in the above, oil content and sludgd deposition are at reactor bottom;
5) separate discharging: when supernatant liquor reaches following each index: when positive phosphorus≤1ppm, oil＜15ppm, suspended substance＜50ppm., COD＜700PPm, clear water is drained into the turbid recycle system (being the sewage second-level treatment system) handles the back again and discharge; Oil content and mud enter the mud underground tank from reactor bottom.
In the aforesaid method, preferred CaO of dephosphorization agent or Ca (OH)
2Preferred N8100 of water treatment agent and ULTIMER7751 with oil removing, flocculation, cohesion, the preferred 100-150ppmN8100 of its addition, 50-100ppmULTIMER 7751, most preferably 140ppmN8100,60ppmULTIMER 7751, and the interpolation order preferably adds N8100 earlier, adds ULTIMER7751 again.
The economical treatment unit of a kind of waste magnetic suspending liquid, it comprises waste magnetic suspending liquid hold-up vessel, reactor and mud underground tank, wherein, be connected by the pipeline that is provided with sump pump and valve between reactor and the waste magnetic suspending liquid hold-up vessel, be connected by the pipeline that is provided with sludge pump and valve between mud underground tank and the reactor.
In the above-mentioned reactor stirrer is installed.Reactor can be established two, the using and the reserved.
Design of the present invention and principle are as follows:
The concentration of waste magnetic suspending liquid is generally all very high, waste magnetic suspending liquid is handled very difficulty of emission standard with single treatment process, so the present invention has adopted the process sequence of SBR (sequencing batch active sludge) technology of similar sewage disposal.What the present invention was different is that inflow, reaction, precipitation, separation discharging are all carried out in same container, promptly realizes all treating processess in single-processor.Its main technique is: at first by adding chemical agent, make itself and phosphate anion generation chemical reaction, generation calcium phosphate precipitation thing is removed most of phosphate radical; Secondly, the ULTIMERT product that selection conforms to the magnetic flaw detection ink characteristic, and by suitable stirring, reduce oil, suspended substance isoconcentration, by breakdown of emulsion mechanism, make oil in water emulsion and dissolving oil from water separate and removed, and by mechanism such as contact flocculation, electrically neutralization, adsorption bridgings, make impurity such as water-borne glue body, fluorescent material take off the flco that surely is agglomerated into the alumen ustum shape rapidly, under action of gravity, precipitate.After impurity such as the phosphate radical in the water, oil content and colloid obtained removing, chemical oxygen demand (COD) also reduced simultaneously.In coagulating, use the contact flocculation technology, strengthened coagulation effect.Clear water water quality after the processing reaches the requirement that general traditional sewage second-level is handled influent quality; Clear water mix with the waste water of sewage second-level treatment system one handle again after, discharge water reaches environmental requirement (positive phosphorus≤1ppm, oil＜5ppm, suspended substance＜50ppm, COD＜100PPm.).
Though method of the present invention is similar to the part operation of the common SBR technology that is used for sewage disposal, on principle, be different from the biochemical processing method of SBR fully.If this waste magnetic suspending liquid waste water is handled with the SBR technology, then at first to consider the nutrition source of microorganism: the proportioning (100: 5: 1) of carbon nitrogen phosphorus.SBR belongs to the aerobic biochemical treatment technology, at first will adopt the pre-treatment in early stage that chemical oxygen demand (COD) is dropped to below the 2000mg/L, and the ratio of biochemical oxygen demand (BOD) and chemical oxygen demand (COD) could directly be handled in 0.2～0.45 with SBR.The chemical oxygen demand (COD) of waste magnetic suspending liquid water quality is 14200mg/L, and clearly the nutritive element of this water quality does not satisfy the needs of microorganism growth.If handle this waste magnetic suspending liquid with SBR, then need the pre-processing device in early stage, and need in water, to add nutritive element, the carbon N/P ratio example that microorganism growth is needed is about 100: 5: 1.In addition, also to increase source of the gas, set up a cover aerating apparatus, for microorganism growth provides oxygen.Therefore, no matter from investment angle, floor space, or the operational management aspect, all be not suitable for handling waste magnetic suspending liquid with the common process of SBR technology.
Principle of the present invention is to adopt physico-chemical process to dispose of sewage, and without culturing micro-organisms, it is littler therefore to compare floor space with the biochemical technology of SBR, and the condition of technology implementation is more simple, not only has economically, and easy to operate, and operational management is more convenient.The materilization freatment method that the present invention adopts is that the adjustment by workshop section and processing parameter realizes separating of various impurity and water in a treater.And,, on treatment process, be used in combination proprietary ULTIMER at the characteristic of waste magnetic suspending liquid
TMProducts scheme realizes separating of various impurity and water.This ULTIMER
TMProduct is different from single flocculation agent, flocculant product, to become key mode and bridging action in the suspended substance surface, colloidal titration detects usually less than residual polymer in flocculation process, and it both can be used as flocculation agent, can be used as flocculation agent again, and make simple to operate, expense reduce.
See Fig. 3, technical process of the present invention comprises the operation by following order:
Sewage flows into, dephosphorization (formation calcium phosphate precipitation), and the coagulating precipitate and separate is separated discharging, and clear water returns the turbid recycle system and handles the back discharging again.
More than the function of each operation be described below:
1, sewage flows into: sewage elder generation injecting reactor, react again after filling with, and in this sense, reactor plays the effect of equalizing tank, and therefore, reactor has certain shock resistance to the change of water quality, the water yield.
2, dephosphorization: add dephosphorization agent, stirring reaction forms calcium phosphate precipitation.After adding dephosphorization agent, remove phosphate radical on the one hand, ready for the reaction of next process contact flocculation on the other hand.
3, coagulating: this is a topmost procedure of the present invention.After generating calcium phosphate precipitation, form certain suspension slime layer in the reactor, at this moment open dosing pump and inject the water treatment agent that finite concentration has oil removing, flocculation, cohesion, start stirrer simultaneously, medicament and water are fully reacted, to reach water and separate impurities.Little flocculation particle and body refuse that stirring helps in the water carry out contact flocculation, strengthen the coagulating effect, and churning time is pressed coagulation effect and decided.
4, precipitate and separate: stop to stir, mixed solution is remained static, sedimentation time is generally greater than 1 hour.Oil content, mud and clear water separate, clear water in the above, oil content and sludgd deposition are at reactor bottom.(if after handling, oil content is floated on supernatant liquor, for the processing of oil content one cover skimming plant need be installed in addition then, will increase greatly between cost and working hour).ULTIMER
TMBe used with flocculation agent and address this problem, make oil content be deposited on reactor bottom, enter the mud underground tank, thereby reduced cost and operating time with mud.
5, separate discharging: clear water enters the sewage second-level treatment system and handles the back discharging again from the reactor middle and lower part; After treating that clear water has been arranged, oil content and mud enter the mud underground tank from reactor bottom.
Beneficial effect of the present invention is as follows:
The water quality that adopts method of the present invention to handle satisfies the requirement of turbid recycle system influent quality, can be by the back up to standard discharging of turbid circular treatment.Simultaneously, the present invention have reduce cost of investment, batch processed amount big, be suitable for advantages such as on-the-spot utilization, simple to operate, convenient operating maintenance, not only satisfied the demand of producing, also satisfied the needs of environmental protection.
Fig. 1 is the economical processing technological flow and the setting drawing of waste magnetic suspending liquid of the present invention.Fig. 2 is the process flow sheet of the pre-membrane filtration treatment technology of sorbent material in the past.Fig. 3 is the economical processing technological flow figure of waste magnetic suspending liquid of the present invention.Fig. 4 is the process flow sheet of embodiment 1.
Description of drawings
Below in conjunction with drawings and Examples and experimental example, the invention will be further described for the application test example.
Embodiment
Embodiment:
As shown in Figure 1, the economical treatment unit of waste magnetic suspending liquid of the present invention comprises: waste magnetic suspending liquid hold-up vessel a 1 (volume 10m
3), promptly be used for storing waste magnetic suspending liquid stoste; Two reactor 2 (volume 10m
3, the using and the reserved), and be connected by the pipeline that is provided with sump pump 4 and valve 5 between the waste magnetic suspending liquid hold-up vessel; Two stirrers 6 are installed in the reactor respectively; One mud underground tank 3 is used for storing and handles the back waste residue, is connected by the pipeline that is provided with valve 8 with reactor bottom, is connected by the pipeline that is provided with sludge pump 7 and valve 9 with reactor head.
The operation flow process of this device is seen Fig. 4.
Now the function with each operation is described below:
1, sewage flows into: after treating the full waste magnetic suspending liquid hold-up vessel of sewage storage, start sump pump and squeeze into reactor.
2, add dephosphorization agent unslaked lime (CaO):
Following reaction: CaO+H takes place after adding unslaked lime
2O → Ca (OH)
2
3Ca
2++2PO
4 3-＝Ca
3(PO
4)
2↓
Add unslaked lime and stir simultaneously, generate Ca
3(PO
4)
2Precipitation is removed phosphate radical on the one hand, and is ready for the reaction of next process contact flocculation on the other hand.By the add-on of control dephosphorization agent, regulate about PH to 10, so that the positive phosphorus value after the dephosphorization is smaller or equal to 1ppm.
3, coagulating: after generating calcium phosphate precipitation, form certain suspension slime layer in the reactor, at this moment open dosing pump and inject the water treatment agent that finite concentration has oil removing, flocculation, cohesion, start pulpboard formula stirrer simultaneously and carry out stirring reaction, make each impurity cohesion in the water, form cotton-shaped alumen ustum, and constantly sedimentation.Little flocculation particle and body refuse that stirring helps in the water carry out contact flocculation, strengthen the coagulating effect.Churning time is 15 minutes left sides
4, precipitate and separate: stop to stir, mixed solution is remained static, sedimentation time is about 2 hours.Oil content, mud and clear water separate, clear water in the above, oil content and sludgd deposition are at reactor bottom.
5, separate discharging: when supernatant liquor reaches following each index: positive phosphorus≤1ppm, oil＜15ppm, suspended substance＜50ppm., COD＜700PPm, clear water come out from the reactor middle and lower part (the figure shown in the A) enter the seamless turbid recycle system reuse of the steel pipe (potentiality of utilizing the turbid recycle system that COD is handled, make again water quality after handling reach the emission standard of national requirements for environmental protection: positive phosphorus＜1ppm, oil＜5ppm, suspended substance＜50ppm, COD＜100ppm), after treating that clear water has been arranged, oil content and mud enter mud underground tank 3.
Illustrate:, then can squeeze into reactor and handle again by sludge pump 7 if mud underground tank water ratio is bigger; If clear water water quality defective (among the figure shown in the B) then enters the waste magnetic suspending liquid hold-up vessel, handle once more, up to qualified.
Experimental example:
In order to select the best water treatment agent of effect, water treatment agent N3683, N3457, N7768, N8100 and ULTIMER 7751 that the present invention selects for use company of U.S. nail (unit of length) section (Nalco) to produce, useless magnetic liquid has been carried out a series of laboratories bottle cup tests (Jar Test), and the result is as follows:
(water sample: waste magnetic suspending liquid; Volume of water sample: 1000ml)
Test one
Remarks: 1. 2. 3. be order of addition of ingredients.
Test two
Remarks: 1. 2. 3. be order of addition of ingredients.
Test three
Remarks: 1. 2. 3. be order of addition of ingredients.
Can find out from above comparison of test results, add 0.2%Ca (OH) earlier
2, adding 100-150ppmN8100 again, the water treatment effect that then adds 50-100ppmULTIMER 7751 schemes is best.And this scheme dosing and expense are lower than 8 yuan/ton, have very big economy and operability.
Therefore, select for use following preferred plan to carry out field application test:
| Water treatment agent | Function | Add dosage |
| Ca(OH) 2 | Dephosphorization agent is regulated about PH to 10 | In right amount |
| N8100 | Organic degreaser | 100-150ppm |
| ULTIMER?7751 | Flocculation, flocculation agent | 50-100ppm |
The application test example:
Adopt technical process embodiment illustrated in fig. 1 and device to handle waste magnetic suspending liquid, the medicament scheme of adding is selected for use: add 0.2%Ca (OH) earlier
2The stirring reaction dephosphorization adds the oil removing of 140ppmN8100 stirring reaction again, then adds 60ppmULTIMER 7751 stirrings and carries out flocculation reaction.
Waste magnetic suspending liquid is through after the above-mentioned processing, and clear water water quality reaches following standard:
| Project | Before the processing | After the processing |
| Turbidity/NTU | 1392 | 5.3 |
| Oil-contg/ppm | 1530 | 14.3 |
| COD/ppm | 14200 | ＜350 |
| Positive phosphorus/ppm | 126 | 0.5 |
| Suspended substance/ppm | 2320 | ＜50 |
| Ammonia nitrogen/ppm | 85 | ＜15 |
Can find out that from last table waste magnetic suspending liquid water quality after treatment is greatly improved, at first be that turbidity obviously descends, and the concentration of suspension in the illustrative system reduces significantly; Secondly, positive phosphorus concentration drops to≤1ppm from 126ppm, has descended 100 times; Oleaginousness drops to＜15ppm from 1530ppm, has also descended 100 times.Water quality after this processing satisfies the requirement of turbid recycle system influent quality, can be by the back up to standard discharging of turbid circular treatment.
Below be waste magnetic suspending liquid, adopt the clear water quality that can reach after method of the present invention and the device processing at different impurities content:
| Project | Before the processing | After the processing |
| Turbidity/NTU | 50-2000 | 5-30 |
| Oil-contg/ppm | 10-1900 | 5-15 |
| COD/ppm | 500-25000 | 300-700 |
| Positive phosphorus/ppm | 10-260 | 0.3-1 |
| Suspended substance/ppm | 100-2500 | 10-50 |
| Ammonia nitrogen/ppm | 50-100 | 8-14 |
Repeatedly the application test result shows, the present invention adopts Ca (OH) according to the method described above
2, 7,751 three kinds of medicaments of N8100, ULTIMER select the proportioning of different concns to cooperate processing, magnetic flaw detection ink water quality is being greatly improved on the basis at present, turbidity obviously descends, suspended substance, COD concentration reduce significantly, and positive phosphorus concentration, oleaginousness can tens times, become hundred times of ground to descend.Water quality after this processing can reach positive phosphorus≤1ppm, oil＜15ppm, suspended substance＜50ppm., COD＜700PPm, satisfy the requirement of turbid recycle system influent quality, can (positive phosphorus＜1ppm, oil＜5ppm, suspended substance＜50ppm, COD＜100PPm.) back discharging up to standard by turbid circular treatment.
Simultaneously, can find out from technology shown in Figure 1 and device, the present invention has that cost of investment is low (to be flowed into, reaction, precipitation, separate each operation of discharging and all carry out in same reactor, facility and place have been saved, and dosing and expense are low), advantages such as batch processed amount big (can handle 10 tons for every batch), simple to operate, convenient operating maintenance, not only satisfy the demand of producing, also satisfied the needs of environmental protection, and economical and practical.
Claims (2)
1. a waste magnetic suspending liquid treatment process is characterized in that it comprises the following steps:
1) sewage flows into: with the waste magnetic suspending liquid injecting reactor;
2) dephosphorization: add dephosphorization agent, remove phosphate radical, regulate pH to 10, make positive phosphorus≤1ppm;
3) coagulating: add water treatment agent, stir, medicament and water are fully reacted with oil removing, flocculation, cohesion;
4) precipitate and separate: stop to stir, mixed solution is remained static, precipitation is separated oil content, mud and clear water, clear water in the above, oil content and sludgd deposition are at reactor bottom;
5) separate discharging: when supernatant liquor reaches following each index: when positive phosphorus≤1ppm, oil＜15ppm, suspended substance＜50ppm., COD＜700ppm, clear water is drained into the turbid recycle system handles the back discharging again, oil content and mud enter the mud underground tank from reactor bottom.
2. waste magnetic suspending liquid treatment process according to claim 1 is characterized in that, described dephosphorization agent is CaO or Ca (OH)
2
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