CN101045587A - Water treatment agent and preparation method for simultaneously removal of suspend solid, nitrate and phosphate - Google Patents

Water treatment agent and preparation method for simultaneously removal of suspend solid, nitrate and phosphate Download PDF

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Publication number
CN101045587A
CN101045587A CNA200710089512XA CN200710089512A CN101045587A CN 101045587 A CN101045587 A CN 101045587A CN A200710089512X A CNA200710089512X A CN A200710089512XA CN 200710089512 A CN200710089512 A CN 200710089512A CN 101045587 A CN101045587 A CN 101045587A
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powder
stage
sub
water conditioner
phosphorus
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CN100544817C (en
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李春锡
方大山
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GCMKOREA CO Ltd
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/30Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention relates to water treatment agent, especially powder and liquid water treatment agent which can not only remove suspend solid, nitrate, phosphate and stench, but also minimize secondary pollution and slurry suspension using natural minerals.The preparation method of liquid water treatment agent for removing suspend solid, nitrate,phosphate and stench in the invention includes the following seven stages:smash and grind wheat loess,calcite, clamshell, limestone, feldspar filter sand, zeolite, germanium, allanite and fiery rock and form into tiny powder; add K<SUB>2</SUB>SiF<SUB>6</SUB> weighing 0.1-5wt% of the total powder and CaCl<SUB>2</SUB> and BaCl<SUB>2</SUB> weighing 10-15wt% of the total powder in turn; calcine at 600degrees in the heating furnace for 5 hours; carry out acid treatment with citric acid to the calcined powder at 60degrees for 2 hours; grind the powder after acid treatment into tiny powder; filtrate powder whose size is below 10mum from grinded powder by hydrocyclone; add the filtrated powder into deionized water, rotate and stir at high speed.

Description

Remove suspended substance, nitrogen, phosphorus and malodorous water conditioner method for making and water conditioner
Technical field
The present invention relates to water conditioner, especially relate to a kind of utilize natural mineral, can remove suspended substance, nitrogen, phosphorus and stench and can make secondary pollution and mud suspend minimized powder and aqueous water conditioner again.
Background technology
Along with population increase, industry development and growth in the living standard, the output that various waste water such as waste water hold in sanitary sewage, industrial wastewater, family sharply increases.This waste water flow in the river, not only again can not make various waters with river, and contaminated water quality can be perched to biology and done great damage.
Recent small-sized village water drain purifying problem is quite paid close attention to as a social concern.The village water drain is the outer interval, type rivers and creeks, water route that does not have vacant lot on the ground of dike, is the form that can see in the little rivers and creeks of major part.The sewage separation facilities or the equipment that dams can't be set in the dike other places under this structure, usually it is used as the draining road as water drain, thereby water pollution be worsened.
The main cause of this water pollution has: water, fecaluria under the life of discharging from family and buildings; Industrial wastewater from factory and public institution's discharge; Hold fecaluria from livestock products waste water, family that the livestock products facility is discharged; The water of discharging from crop land, forest during rainfall; From the campsite, oil, sewage, food waste, the various rubbish of facility thing discharges waterborne such as fishing field, public place of entertainment; The agricultural chemicals of discharging, fertilizer etc. from farmers' or golf field.
Organic substances such as a large amount of suspended substances that contain in the especially this waste water, nitrogen, phosphorus are the eutrophication that promote the breeding of algae and growth, promotion river or lake water, produce the holocoenotic main cause of destruction of stench etc.And this ruined ecosystem almost can't be recovered, and perhaps it recovers to need to drop into a large amount of time and expense, therefore is necessary to remove the main cause of this pollution in advance.
But at present, when handling the water that has polluted, must possess the suspended substance of removing, nitrogen, phosphorus and malodorous various facility, the equipment enlarging that causes thus can produce a large amount of construction costs, investment cost and running expenses such as expense are bought in the soil.
In addition, conventional art is owing to add pharmaceutical chemicals, thereby causes secondary pollution.For removing the secondary pollution source, following water treatment practitioner need handle afterwards, has formed bigger burden so economically.And, need the processing costs of overspending, and need to separate little flocs unit owing to produce a large amount of mud.In addition, utilize method of microorganism to have problems such as non-Economy, non-efficiency, also be subjected to the influence of external conditions.
Summary of the invention
For addressing the above problem, the objective of the invention is to: the water conditioner that the manufacture method of a kind of powder and aqueous water conditioner is provided and produces thus, thereby realization can be removed suspended substance, nitrogen, phosphorus and stench simultaneously and be improved the water treatment effect, and mud suspension amount is minimized.
Of the present invention have a powder water conditioner manufacture method of removing suspended substance, nitrogen, phosphorus and stench effect, it is characterized in that: comprise following five stages, pulverize and grind the stage that forms micro powder thereby wheat loess, calcite, clam shell, Wingdale, feldspathic are crossed filter sand, zeolite, germanium, orthite, fiery rock; In above-mentioned powder, add the K of total powder 0.1~5wt% successively 2SiF 6, total powder 10~15wt% CaCl 2And BaCl 2Stage; In process furnace, under 600 ℃ of conditions, calcine 5 hours stage; Under 60 ℃ condition, utilize citric acid that incinerating powder is carried out 2 hours acid-treated stages; To grind to form through acid-treated powder the stage of micro powder.
Another feature of the present invention is: the mixture ratio of above-mentioned mineral is that wheat loess 17-23wt%, calcite 9-11wt%, clam shell 9-11wt%, Wingdale 9-11wt%, feldspathic are crossed filter sand 17-23wt%, zeolite 9-11wt%, germanium 6-8wt%, orthite 6-8wt%, fiery rock 5-7wt%.
Another feature of the present invention is: the moiety of above-mentioned powder water conditioner is SiO 2Account for 45~55% of weight, CaCO 3Account for 15~25% of weight, Al 2O 3Account for 15~25% of weight, MgO accounts for 0.01~5% of weight, Fe 2O 3Account for 0.01~4% of weight.
Of the present invention have an aqueous water conditioner manufacture method of removing suspended substance, nitrogen, phosphorus and stench effect, it is characterized in that: comprise following seven stages, pulverize and grind the stage that forms micro powder thereby wheat loess, calcite, clam shell, Wingdale, feldspathic are crossed filter sand, zeolite, germanium, orthite, fiery rock; In above-mentioned powder, add the K of total powder 0.1~5wt% successively 2SiF 6, total powder 10~15wt% CaCl 2And BaCl 2Stage; In process furnace, under 600 ℃ of conditions, calcine 5 hours stage; Under 60 ℃ condition, utilize citric acid that incinerating powder is carried out 2 hours acid-treated stages; To grind to form through acid-treated powder the stage of micro powder; From the powder that has ground, utilize swirler to filter out the stage of the following powder of 10 μ m; The powder that has screened is added to the stage of carrying out the high speed rotating stirring in the deionized water.
Another feature of the present invention is: the mixture ratio of above-mentioned mineral is that wheat loess 17-23wt%, calcite 9-11wt%, clam shell 9-11wt%, Wingdale 9-11wt%, feldspathic are crossed filter sand 17-23wt%, zeolite 9-11wt%, germanium 6-8wt%, orthite 6-8wt%, fiery rock 5-7wt%.
Description of drawings
Fig. 1 is the particle size distribution figure of powder water conditioner particle of the present invention;
Fig. 2 is the SEM picture of powder water conditioner particle of the present invention;
Fig. 3 is that the electrokinetic potential of powder water conditioner particle of the present invention is measured curve.
Embodiment
Manufacture method to powder of the present invention and aqueous water conditioner is elaborated below.
At first, thus wheat loess, calcite, clam shell, Wingdale, feldspathic are crossed filter sand, zeolite, germanium, orthite, fiery rock pulverize and grind and form micro powder.In this process, adopt ore to pulverize, and utilize the zirconium ball mill that the mineral of pulverizing are ground to form hundreds of nm to tens of μ m.
Consider economy, starting material supply and demand problem, suspended substance, nitrogen, phosphorus, the malodorous water treatment effect that draws in effect and a large amount of test-results of removing simultaneously, the mixture ratio of each mineral preferably wheat loess 17-23wt%, calcite 9-11wt%, clam shell 9-11wt%, Wingdale 9-11wt%, feldspathic is crossed filter sand 17-23wt%, zeolite 9-11wt%, germanium 6-8wt%, orthite 6-8wt%, fiery rock 5-7wt%.Medical stone content is as surpassing 23wt%, and its viscosity increases and is difficult to disperse in the water that pollutes.If but do not reach 17wt%, the unfavorable problem of condensation effect will appear.Clam shell and Wingdale are used to adjust the pH value, if its amount too much, the pH value is too high, and its amount is too small, and the pH value is low excessively.If the amount of the potassium that adds, calcite, zeolite, germanium, orthite, fiery rock is very few, then not to suspended substance, nitrogen, phosphorus, the malodorous effect of removing, and if the amount of adding is too much, then can only remove part suspended substance, nitrogen, phosphorus and stench.
Secondly, in above-mentioned powder, add K successively 2SiF 6, CaCl 2, BaCl 2Usually, making the calcining temperature of the specific surface area maximization of preparation is 1,200 ℃, but this smelting furnace is uncommon, and also there are adverse factors in expense or energy aspect.For overcoming this problem, add K 2SiF 6As flux, can under lower temperature, calcine like this.The amount of adding is the 0.1-5% of total powder weight preferably.If its quantity not sufficient 0.1% does not just have the effect as flux, if but, just do not have economy above 5%.When powder disperses,, add the CaCl of total powder weight 10-15% for obtaining dispersion effect preferably in the water that pollutes 2, BaCl 2Thereby, make the repulsive force maximization between the powder particle, prevent that powder particle from assembling under liquid state.If the amount of adding is below 10%, will occur condensing and sedimentary phenomenon between particle, if surpass 15%, with respect to its expense, the raising of effect is not obvious.
Then, in process furnace, under 600 ℃ of conditions, carry out 5 hours calcining.Treat to use citric acid (C after calcining is finished 6H 8O 7) under 60 ℃, carry out 2 hours acid treatment, afterwards with it with distilled water wash and carry out drying.By calcination process, the specific surface area of particle obtains maximization, and has reduced calcining temperature owing to adding flux, calcines with 600 ℃ temperature at least also can reach its intended purposes in 5 hours.Carry out acid-treated purpose and be to make the coarse particle surface in calcining back to become smooth, thereby prevent that physical and chemical performance descends between particle, and can remove the part operation and carry out the organism that may flow in the process.Utilize the general weak acid of citric acid for example etc. to be fit to, test-results shows, stirs with water after 2 hours the acid treatment carrying out under 60 ℃, at this moment demonstrates best efficient on electric conductivity.
Utilize the air spray Ginding process that the exsiccant powder is ground and make it form micro powder, just can form powder water conditioner of the present invention.Fig. 1 is the particle distribution figure of powder water conditioner, and as can be seen from the figure it is made up of very small particle.Fig. 2 is the SEM picture of powder water conditioner, can know that powder has the form of hexagonal structure from picture, and they have negative charge thereby pulling force is powerful, thereby plays the safe of mud and suppress the effect that mud suspends.
The moiety of this powder water conditioner is SiO 2Account for weight 45~55%, CaCO 3Account for weight 15~25%, Al 2O 3Account for weight 15~25%, MgO account for weight 0.01~5%, Fe 2O 3Account for 0.01~4% of weight.
In addition, for making aqueous water conditioner, after above-mentioned acid treatment, with the air spray abrasive method exsiccant powder being ground is micro powder below the 10 μ m.By calcination process, the specific surface area of particle obtains maximization, thereby has the good adsorption ability, and grinds by air spray, and powder forms the following small-particle of 10 μ m, makes contact area maximization in the water.
Utilize swirler from the powder that grinds, to filter out small-particle below the 10 μ m.The optimum size (theoretical value) that can guarantee the dispersion stabilization of preparation is more than the 0.12 μ m, but also can guarantee dispersion stabilization below drawing several μ m to 10 μ m in the test-results.Therefore only use the following particle of 10 μ m to make aqueous water conditioner, the above particle of 10 μ m is then pulverized again.
At last, the micro powder that has ground is put in the deionized water, stirred at a high speed with the speed more than the 300RPM and form aqueous water conditioner.The amount of deionized water is a fully dissolved degree of the micro powder that ground, can adjust its concentration according to the pollution level of sewage, waste water.Usually, the powder of putting into about about 10kg in 1 ton of deionized water is advisable.
The water treatment effect of water conditioner of the present invention is that the present invention utilizes the ammoniacal liquor degassing method to remove denitrification.Ammoniacal liquor degassing ratio juris is to work as NH 4 +Ion and NH 3Equilibrium equation (equation 1) in pH value be increased to 7 when above, on the left of its balance is shifted to, thus NH 4 +Ion is converted into NH 3, at this moment stir waste water it is outgased in atmosphere, improve the pH value with this, Wingdale and clam shell play such effect.
[equation 1]
NH 3+H 2ONH 4 ++OH -
The composition of contained abundant aluminium, iron, calcium and magnesium obtains ionization and is converted into aluminium salt (Al in the water conditioner of the present invention 3+), molysite (Fe 3+), calcium salt (Ca 2+), magnesium salts (Mg 2+).By this metal ion species, phosphoric acid salt is with Al (PO 4), Fe (PO 4), Ca 3(PO 4) 2Form obtain the precipitation and remove, the organic phosphine of organism particle shape also can be condensed, the reaction formula of each condensing agent is as follows.
[equation 2]
Al 3++PO 4 3-→Al(PO 4)
[equation 3]
Fe 3++PO 4 3-→Fe(PO 4)
[equation 4]
3Ca 2++2PO 4 3-→Ca 3(PO 4) 2
Congealing reaction be by physics move with these two successive dynamic processes such as chemisorption in the phenomenon that produces.It is that surface with a certain colloidal particle moves on the surface of other colloidal particles that physics moves, and effects such as the shearing force by Brown motion, solution, gravity take place.
Reactive force and the distance between the particle between two particles are the funtcional relationship that is inversely proportional to, and move the balance of formed new strength according to physics, produce two particles and obtain the reaction of agglomerative chemisorption.
This physics moves with chemisorption and reacts owing to form in water, will produce the congealing reaction of colloidality suspended substance, eutrophication material and algae on the particle of powder.
Powder water conditioner of the present invention has micropore by the pulverizing and the calcining of natural matter, thereby the absorption of colloidality suspended substance is removed.
In addition, also contain some TiO in the water conditioner of the present invention 2, this TiO 2As photocatalyst, the irradiation that obtains sunlight or luminescent lamp presents powerful deodorization function afterwards, can remove deammoniation, formaldehyde, hydrogen sulfide etc. and cause malodorous main cause material.
Compare with existing natural zeolite, water conditioner of the present invention has reduced SiO 2Content, thus the displacement consumption of salt reduced, and add clam shell and improve alkalescence, thereby make the total charge of particle surface change about pH2 into from 0 electric charge, cation exchange capacity (CEC) is good in the pH of broad scope.(with reference to Fig. 3)
Embodiment
Adopt wheat loess 3.6kg, calcite 1.8kg, clam shell 1.8kg, Wingdale 1.8kg, feldspathic to cross filter sand 3.6kg, zeolite 1.8kg, germanium 1.26kg, orthite 1.26kg, fiery rock 1.08kg respectively, pulverize, utilize the zirconium ball mill grinding to become hundreds of nm again to tens of μ m.Add K at this 2SiF 60.54kg, put into CaCl again 2And BaCl 21.9kg.In process furnace, under 600 ℃ of conditions, carry out 5 hours calcining afterwards, with citric acid after carrying out 2 hours acid treatment under 60 ℃ of conditions with it with distilled water wash and carry out drying, then it is carried out air spray and grinds and form the powder water conditioner.And the fine particle that ground added in the deionized water, stir with the speed of 300RPM and obtain aqueous water conditioner.
Powder that utilization forms thus and aqueous water conditioner are tested and can be drawn following test-results.
Adopt 1L sewage respectively, put into powder and the aqueous water conditioner of 1mg respectively, the result who tests after 10 minutes.
[table 1]
Test subject Before the processing After the powder water conditioner is handled After aqueous water conditioner is handled
COD 102.8 67.5 62.9
BOD5 337.5 71.8 67.8
T-N 129.13 106.65 84.17
T-P 11.00 4.57 2.66
Fe 1.22 1.30 1.86
Mn 0.06 0.06 0.02
Zn 0.26 0.50 0.93
Cu 0.14 0.14 0.13
(notes) test the result who obtains according to water pollution engineering test method.
From The above results, as can be seen, use powder and aqueous water conditioner all can improve water quality.The particular significant effect of especially aqueous water conditioner.
And when using powder of the present invention and aqueous water conditioner, subsidiary have deodorization functions, and its test-results as shown in Figure 2.
[table 2]
Test subject Time spent (branch) Blank concentration (ppm) Test portion concentration (ppm) Deodorization rate (%)
The deodorization test Initial stage 500 500 -
30 490 65 87
60 480 45 91
90 460 30 93
120 450 25 94
(notes) are blank 1.: do not put under the state of test portion and measure.
2. test method: KIFA-FI-1004
It is also pretty good to remove malodorous effect from the result as can be seen.
And subsidiary when using powder water conditioner of the present invention bacteria removing effect being arranged, its test-results is as shown in table 3.
[table 3]
Test subject Test portion is distinguished Initial stage concentration Concentration after 24 hours Quiet bacterium decrement
The colibacillus antibacterial tests Blank 3.0×10 8 8.8×10 8 -
The powder water conditioner <1.0×10 4 99.9
The pseudomonas aeruginosa antibacterial tests Blank 2.0×10 7 6.2×10 7 -
The powder water conditioner <1.0×10 3 99.9
(notes) are blank 1.: do not put under the state of test portion and measure
2. test method: KIFA-FI-1002
Use water conditioner of the present invention, not only can remove suspended substance, nitrogen, phosphorus and stench simultaneously, and utilize natural mineral that secondary pollution is minimized, and the pollution substance that can condense makes its precipitation, thereby suppress the suspension of mud to greatest extent.

Claims (7)

1. one kind is used to remove suspended substance, nitrogen, phosphorus and malodorous powder water conditioner manufacture method, it is characterized in that: comprise following five stages, pulverize and grind the stage that forms micro powder thereby wheat loess, calcite, clam shell, Wingdale, feldspathic are crossed filter sand, zeolite, germanium, orthite, fiery rock; In above-mentioned powder, add the K of total powder 0.1~5wt% successively 2SiF 6, total powder 10~15wt% CaCl 2And BaCl 2Stage; In process furnace, under 600 ℃ of conditions, calcine 5 hours stage; Under 60 ℃ condition, utilize citric acid that incinerating powder is carried out 2 hours acid-treated stages; To grind to form through acid-treated powder the stage of micro powder.
2. according to claim 1ly be used to remove suspended substance, nitrogen, phosphorus and malodorous powder water conditioner manufacture method, it is characterized in that: the mixture ratio of above-mentioned mineral is that wheat loess 17-23wt%, calcite 9-11wt%, clam shell 9-11wt%, Wingdale 9-11wt%, feldspathic are crossed filter sand 17-23wt%, zeolite 9-11wt%, germanium 6-8wt%, orthite 6-8wt%, fiery rock 5-7wt%.
3. one kind is used to remove suspended substance, nitrogen, phosphorus and malodorous powder water conditioner according to claim 1 or 2 described method manufacturings.
4. according to claim 3ly be used to remove suspended substance, nitrogen, phosphorus and malodorous powder water conditioner, it is characterized in that: the moiety of above-mentioned powder water conditioner is SiO 2Account for 45~55% of weight, CaCO 3Account for 15~25% of weight, Al 2O 3Account for 15~25% of weight, MgO accounts for 0.01~5% of weight, Fe 2O 3Account for 0.01~4% of weight.
5. aqueous water conditioner manufacture method that is used to remove suspended substance, nitrogen, phosphorus and stench effect, it is characterized in that: comprise following seven stages, pulverize and grind the stage that forms micro powder thereby wheat loess, calcite, clam shell, Wingdale, feldspathic are crossed filter sand, zeolite, germanium, orthite, fiery rock; In above-mentioned powder, add the K of total powder 0.1~5wt% successively 2SiF 6, total powder 10~15wt% CaCl 2And BaCl 2Stage; In process furnace, under 600 ℃ of conditions, calcine 5 hours stage; Under 60 ℃ condition, utilize citric acid that incinerating powder is carried out 2 hours acid-treated stages; To grind to form through acid-treated powder the stage of micro powder; From the powder that has ground, utilize swirler to filter out the stage of the following powder of 10 μ m; The powder that has screened is added to the stage of carrying out the high speed rotating stirring in the deionized water.
6. according to claim 5ly be used to remove suspended substance, nitrogen, phosphorus and malodorous aqueous water conditioner manufacture method, it is characterized in that: the mixture ratio of above-mentioned mineral is that wheat loess 17-23wt%, calcite 9-11wt%, clam shell 9-11wt%, Wingdale 9-11wt%, feldspathic are crossed filter sand 17-23wt%, zeolite 9-11wt%, germanium 6-8wt%, orthite 6-8wt%, fiery rock 5-7wt%.
7. one kind is used to remove suspended substance, nitrogen, phosphorus and malodorous aqueous water conditioner according to claim 6 or 7 described method manufacturings.
CNB200710089512XA 2006-03-28 2007-03-27 Remove the water treatment agent method for making and the water treatment agent of suspension, nitrogen, phosphorus and stench Expired - Fee Related CN100544817C (en)

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KR1020060027995A KR100702065B1 (en) 2006-03-28 2006-03-28 Water treatment particle for simultaneously removal of suspend solid, nitrate and phosphate
KR1020070029036 2007-03-26

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CN112408522A (en) * 2020-11-30 2021-02-26 汕头市麦氧环保科技有限公司 Natural composite wastewater treatment agent and preparation method thereof

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