CN101913676B - Method for removing phosphorus in water by utilizing ferric salt-modified eggshells - Google Patents

Method for removing phosphorus in water by utilizing ferric salt-modified eggshells Download PDF

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CN101913676B
CN101913676B CN2010102448194A CN201010244819A CN101913676B CN 101913676 B CN101913676 B CN 101913676B CN 2010102448194 A CN2010102448194 A CN 2010102448194A CN 201010244819 A CN201010244819 A CN 201010244819A CN 101913676 B CN101913676 B CN 101913676B
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phosphorus
eggshell
egg
modified
shell meal
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CN101913676A (en
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郭照冰
陈天
包春晓
董琼元
周飞
郑正
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Changshu Guli Technology Venture Service Co ltd
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Nanjing University of Information Science and Technology
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Abstract

The invention belongs to the processing field of sewage containing phosphorus, and discloses a method for removing phosphorus in water by utilizing ferric salt-modified eggshells. The method comprises the following steps: the modified process of the eggshell: mixing 0.1-0.5mol/L of ferric salt solution and eggshell power at the temperature of 10-60 DEG C, wherein the mass ratio of substance amount of ferric salt to the eggshell powders is 0.001-0.0015mol/g; subsequently continually stirring for 24h; filtering; finally placing into an oven; drying at the temperature of 100-105 DEG C; sieving through a 100-mesh sieve to obtain the modified eggshell powders; and placing the modified eggshell powders into a dryer for later use; and phosphorous removal process in sewage: adding 0.1-1g of modified eggshell powders to 100mL of solution containing phosphorus with the concentration of 0.2-50mg (P)/L, wherein the pH of the solution is 3-10; performing constant temperature vibration at the temperature below 10-40 DEG C in the speed of 50-200r/min; and carrying out 0.45 mu m filter membrane after vibrating for 10min-6h.

Description

Utilize ferric salt-modified eggshells to remove the method for phosphorus in the water
One, technical field:
The present invention relates to a kind of method of utilizing ferric salt-modified eggshells to remove phosphorus in the water, belong to the process field of phosphorus-containing wastewater.
Two, background technology:
Frequent day by day along with mankind's activity, the phosphor resource that can directly utilize just constantly reduces, and the phosphorus concentration in the water bodys such as rivers and lakes is in continuous increase.The phosphorus that water body weight increases is constantly grown organism such as algae, causes body eutrophication.Body eutrophication to Human's production life influence greatly, therefore produced the technology and method of various dephosphorization, but these methods all have shortcoming more or less, and this makes and seek efficiently, cleans, cheap phosphorus removal method becomes a focus of water treatment already.
The phosphorus treatment process is varied in the water, and electrolysis has good effect of removing from physical methods such as, reverse osmosiss to phosphorus, but cost is often higher.Cheap biological method non-secondary pollution, but stable water outlet is relatively poor, also responsive to outside atmosphere.In the method for chemical dephosphorization, coagulation and absorption are mainstream technologys always.Coagulation Method has treatment effect preferably to phosphorus, but consequent refuse can't be recycled.Absorption method also has treatment effect preferably to phosphorus, and the waste residue that adsorption process produces can also be reused by desorption process.Therefore relatively Coagulation Method, people more expect to adopt the phosphorus of absorption method in dewatering.In absorption method, how to select phosphorus to remove strong, the with low cost valency of ability, method easy and simple to handle, be the focus of water treatment research always.Active aluminum, zeolite be because of having bigger specific surface area, obligate absorption, advantage such as porous and being widely used, but insufficient be that these prices of raw and semifnished materials are higher, and zeolite is difficult to resolve and analyses phosphorus.This water purification waste material of alum slag, its wide material sources also demonstrate phosphorus treatment effect preferably in secular practice, but in the water treatment procedure, usually can be in water the stripping harmful ion, form secondary pollution.Consider that trivalent metal such as iron, aluminium salt has the ability of phosphorus removal preferably in the coagulating agent.Therefore, we are in conjunction with these two kinds of methods, in the hope of preparing novel dephosphorization material.
Three, summary of the invention:
In order to improve the removal ability of discarded eggshell to phosphorus in the waste water, the invention provides a kind of method of utilizing ferric salt-modified eggshells to remove phosphorus in the water, eggshell after this method modification has that phosphor-removing effect is good, cost is inexpensive, the source is abundant, advantage such as easy and simple to handle, the theory that meets waste recycling has good benefits in environment and economic benefit.
Technical scheme of the present invention is as follows:
A kind of method of utilizing ferric salt-modified eggshells to remove phosphorus in the water, it is characterized in that: this method may further comprise the steps:
1) modifying process is as follows:
Under 10-60 ℃, 0.1-0.5mol/L iron salt solutions and egg-shell meal are mixed, the amount of substance of molysite and the mass ratio of egg-shell meal are 0.001-0.0015mol/g; Continue stirring subsequently, stir the 24h after-filtration, put into baking oven at last, dry under 100-105 ℃, cross 100 mesh sieves, get the modification egg-shell meal, it is standby to put into moisture eliminator;
2) dephosphorization process is as follows:
The above-mentioned modification egg-shell meal of 0.1-1g added in the 100mL solution containing phosphate that concentration is 0.2-50mg (P)/L carry out Static Adsorption, the pH of solution is 3-10, in temperature is to carry out the constant temperature vibration with the speed of 50-200r/min under 10-40 ℃, crosses 0.45 μ m filter membrane behind the 10min-6h.
Above-mentioned iron salt solutions is selected iron(ic) chloride or iron nitrate solution for use.
The pretreatment process of eggshell: the discarded Ovum crusta Gallus domesticus that will reclaim cleans, and removes inner membrance, and 100 mesh sieves are crossed in dry back, and particle diameter is dried down at 102-105 ℃ less than 100 purpose Ovum crusta Gallus domesticus powder, put in the moisture eliminator standby.
The main component of discarded eggshell is a lime carbonate, and its wide material sources the phosphorus in the water body is had certain removal ability, but its adsorptive capacity are relatively low.Molysite has better removal effect to phosphorus, and the source is abundant, cheap.Utilize ferric salt-modified eggshells, make eggshell surface load molysite, can increase the active sites of eggshell surface, improve the electrostatic adhesion ability of eggshell phosphorus.The present invention is in the hope of improving the dephosphorization ability of eggshell by be coupled discarded eggshell and molysite.
Beneficial effect of the present invention:
(1) adopt the modified abandoned eggshell of molysite to have the ability of phosphorus removal preferably, its phosphorus adsorptive capacity is increased to 3.54mg (P)/g by 0.3064mg (the P)/g of original unmodified egg-shell meal, and adsorptive capacity has improved more than ten times.This adsorption effect has significant synergistic effect far above the coagulation for phosphorus removal amount sum of equivalent natural egg-shell meal adsorption and dephosphorization amount and equivalent modification usefulness iron ion.
(2) adopt the ferric salt-modified eggshells powder to be fit to apply to have certain antiacid impact capacity in the environment that pH is 3-10.The used molysite of modification eggshell can not be dissolved in the water body, avoids causing secondary pollution of water.
(3) present method has realized refuse reclamation, as the Ovum crusta Gallus domesticus of domestic refuse, by to its simple modification, can realize effective removal of phosphorus in the waste water, realizes changing rejected material to useful resource.
Four, embodiment:
Embodiment 1
The present invention utilizes ferric salt-modified eggshells to remove the method for phosphorus in the water, may further comprise the steps:
1, discarded eggshell pre-treatment:
The discarded eggshell that reclaims is cleaned, remove inner membrance.After being dried, grinding and cross 100 mesh sieves and separate.Particle diameter is dried down at 105 ℃ less than 100 purpose Ovum crusta Gallus domesticus powder, and it is standby to put into moisture eliminator.
2, eggshell modification:
In temperature is under 25 ℃, to the 0.25mol/L of 20mL Fe (NO 3) 3Solution adds the good discarded egg-shell meal of 4g pre-treatment, and continues to stir.The 24h after-filtration is with distilled water diafiltration 4 times.Put into baking oven at last, cross 100 mesh sieves 105 ℃ of dry down backs and separate.
3, modification eggshell dephosphorization:
With the modification egg-shell meal adding concentration of 0.1g is in the 100mL solution containing phosphate of 15mg (P)/L, and the pH that regulates phosphorus solution with NaOH solution is 7, is to carry out the constant temperature vibration with the speed of 150r/min under 25 ℃ in temperature.Cross 0.45 μ m filter membrane behind the 2h.Survey phosphorus concentration in the filtrate with molybdenum-antimony anti-spectrophotometric method, recording the modification egg-shell meal is 3.54mg (P)/g to the adsorptive capacity of phosphorus.
Embodiment 2
Substantially the same manner as Example 1, Fe (NO 3) 3Temperature during the solution modification eggshell changes 60 ℃ into, and the modification egg-shell meal is 3.50mg (P)/g to the adsorptive capacity of phosphorus.
Embodiment 3
Substantially the same manner as Example 1, the 0.4mol/L FeCl of employing 12.5mL 3Solution carries out modification to discarded eggshell, and other is with embodiment 1, and the modification egg-shell meal is 3.58mg (P)/g to the adsorptive capacity of phosphorus.
By embodiment 1,2,3 as can be seen, when discarded eggshell was carried out modification, the height of modification temperature had no significant effect with the phosphorus removal ability of molysite kind to the modification eggshell.
Embodiment 4
In the solution containing phosphate of 100mL 15mg (P)/L, add iron nitrate as coagulating agent (it is 0.000125mol that consumption and embodiment 1 modification egg-shell meal use molysite equivalent), record that phosphorus concentration drops to 14.52mg (P)/L from 15mg (P)/L in the solution, show that iron salt coagulant under this condition is not clearly to the removal ability of phosphorus.
Embodiment 5
The egg-shell meal of 1g is added 100mL, and to contain phosphorus concentration be that 15mg (P)/L, pH is in 7 the sewage, being 100 rev/mins with rotating speed under 25 ℃ temperature stirred 8 hours, carry out Static Adsorption, after absorption finishes, filter through 0.45 μ m filter membrane, recording egg-shell meal is 0.3064mg (P)/g to the adsorptive capacity of phosphorus.Even the concentration of phosphorus continues to increase in the solution in follow-up experiment, its adsorptive capacity does not have bigger variation yet.
By embodiment 1,2,3,4 as can be seen, the modification of molysite has improved the adsorption effect of discarded egg-shell meal to phosphorus greatly, and its phosphorus adsorptive capacity has increased tens of times.
By embodiment 1,4,5 as can be seen, the modification egg-shell meal is removed the phosphorus removal effect sum of effect far above equivalent iron content coagulating agent and natural egg-shell meal to phosphorus in the water, so the modification egg-shell meal has synergistic effect to the removal of phosphorus.
Embodiment 6
Among the embodiment 1, other conditions are constant.The concentration of phosphorus changes 5mg (P)/L in the solution, 10mg (P)/L, record the modification egg-shell meal to the adsorptive capacity of phosphorus be respectively 2.05,2.81mg (P)/g.
By embodiment 1 and 6 as can be seen, along with the raising of starting point concentration, the removal effect of modification egg-shell meal is become better and better.
Embodiment 7
Among the embodiment 1, other conditions are constant, and the concentration of phosphorus changes 5mg (P)/L in the solution, and when adsorption time is 10min, the modification egg-shell meal is 1.52mg (P)/g to the adsorptive capacity of phosphorus; When adsorption time is 30min, the modification egg-shell meal is 1.83mg (P)/g to the adsorptive capacity of phosphorus.
By embodiment 7 as can be seen, along with the prolongation of adsorption time, the modification eggshell is become better and better to the removal effect of phosphorus.
Embodiment 8
Among the embodiment 1, other conditions are constant, and when adsorption temp was 40 ℃, the modification egg-shell meal was 5.18mg (P)/g to the adsorptive capacity of phosphorus; When adsorption temp was 10 ℃, recording the modification egg-shell meal was 3.07mg (P)/g to the adsorptive capacity of phosphorus.
By embodiment 1 and 8 as can be seen, along with the rising of adsorption temp, the modification eggshell is good more to the adsorption effect of phosphorus.
Embodiment 9
Among the embodiment 1, other conditions are constant, and the concentration of phosphorus is 5mg (P)/L in the solution, and when solution containing phosphate pH was 3, the modification egg-shell meal was 3.03mg (P)/g to the adsorptive capacity of phosphorus; When solution containing phosphate pH was 7, the modification egg-shell meal was 2.76mg (P)/g to the adsorptive capacity of phosphorus; When solution containing phosphate pH was 10, recording the modification egg-shell meal was 2.05mg (P)/g to the adsorptive capacity of phosphorus.
By embodiment 9 as can be seen, along with the increase of phosphorus-containing wastewater pH, the remodeling egg-shell meal can be worse and worse to the adsorption effect of phosphorus.
Embodiment 10
The present invention to the modification mode of discarded egg-shell meal is: under 10-60 ℃, 0.1-0.4mol/L iron salt solutions and egg-shell meal are mixed, the amount of substance of molysite and the mass ratio of egg-shell meal are 0.001-0.0015mol/g; Continue stirring subsequently, stir the 24h after-filtration, put into baking oven at last, dry under 100-105 ℃, cross 100 mesh sieves, get the modification egg-shell meal, it is standby to put into moisture eliminator.
Utilize the method for modification egg-shell meal absorption phosphorus: with the modification egg-shell meal adding concentration of 0.1-1g is in the 100mL solution containing phosphate of 0.2-50mg (P)/L, and the pH of solution is 3-10, is that the speed with 50-200r/min is carried out isothermal vibration under 10-40 ℃ in temperature.Cross 0.45 μ m filter membrane behind the 10min-6h, survey the phosphorus concentration in the filtrate at last.
Wherein, when 1. adopting molysite to discarded eggshell modification, modification temperature is 10-60 ℃, and iron salt concentration is any numerical value among the 0.1-0.5mol/L, for example 0.1,0.2,0.4,0.5 etc., and molysite comprises Fe (NO 3) 3, FeCl 3Deng. 2. the starting point concentration of solution containing phosphate can be any numerical value among 0.2-50mg (P)/g, for example 0.2mg (P)/g, 0.6mg (P)/g, 3mg (P)/g, 15mg (P)/g, 30mg (P)/g, 50mg (P)/g etc.PH can make any numerical value among the 3-10, for example, and 3,7,9 etc.Adsorption temp can be 10 ℃, 20 ℃, 30 ℃, 40 ℃ etc., and adsorption time can be the arbitrary data between 10min-6h, as 10min, 30min, 1h, 2h, 6h etc.

Claims (3)

1. method of utilizing ferric salt-modified eggshells to remove phosphorus in the water, it is characterized in that: this method may further comprise the steps:
1) modifying process:
Under 10-60 ℃, 0.1-0.5mol/L iron salt solutions and egg-shell meal are mixed, the amount of substance of molysite and the mass ratio of egg-shell meal are 0.001-0.0015mol/g; Continue stirring subsequently, stir the 24h after-filtration, put into baking oven at last, dry under 100-105 ℃, cross 100 mesh sieves, get the modification egg-shell meal, it is standby to put into moisture eliminator;
2) dephosphorization process:
The above-mentioned modification egg-shell meal of 0.1-1g added in the 100mL solution containing phosphate that concentration is 0.2-50mg/L carry out Static Adsorption, this concentration is with phosphorous concentration measurement, the pH of solution is 3-10, in temperature is to carry out the constant temperature vibration with the speed of 50-200r/min under 10-40 ℃, crosses 0.45 μ m filter membrane behind the 10min-6h.
2. according to the described method of utilizing ferric salt-modified eggshells to remove phosphorus in the water of claim 1, it is characterized in that: described molysite is selected iron(ic) chloride or iron nitrate for use.
3. according to claim 1 or the 2 described methods of utilizing ferric salt-modified eggshells to remove phosphorus in the water, it is characterized in that: the pretreatment process of eggshell: the discarded Ovum crusta Gallus domesticus that will reclaim cleans, remove inner membrance, 100 mesh sieves are crossed in dry back, particle diameter is dried down at 102-105 ℃ less than 100 purpose Ovum crusta Gallus domesticus powder, put in the moisture eliminator standby.
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CN102432083B (en) * 2011-10-28 2013-06-05 上海海洋大学 Method for removing and recovering phosphate in waste water
CN102500337A (en) * 2011-11-21 2012-06-20 大连理工大学 Phosphorus removal adsorbent for modifying oyster shell with iron salt and preparation method as well as application thereof
CN102614854A (en) * 2012-03-31 2012-08-01 复旦大学 Method for preparaing dephosphorized and ferrum-carried activated carbon adsorbent
CN103252216B (en) * 2013-06-03 2014-12-24 江西理工大学 Adsorbent, preparation process thereof and application of adsorbent to purification of ammonia-nitrogen wastewater with medium-low concentration
CN103288164B (en) * 2013-06-25 2015-07-01 南京信息工程大学 A method for synchronous nitrogen and phosphorus removal in sewage by combining modified zeolite and modified eggshell
CN104986822B (en) * 2015-06-19 2017-03-08 华东理工大学 A kind of chemical modification carries the preparation of iron peanut shell dephosphorization material and renovation process
CN106111048A (en) * 2016-07-12 2016-11-16 成都理工大学 One is used for removing phosphatic eggshell loaded nano-iron material and preparation method thereof in water
CN106540649B (en) * 2016-12-07 2019-02-22 福州大学 A kind of green syt of the manganese calcium nano adsorber constructed by egg shell and its application
CN108499521A (en) * 2018-05-04 2018-09-07 南京信息工程大学 The method that phosphorus in water removal is gone using modification with Fe clay
CN110877921A (en) * 2019-08-28 2020-03-13 齐鲁理工学院 Method for removing total nitrogen in water by using modified eggshells
CN111569818A (en) * 2020-05-06 2020-08-25 三峡大学 Drinking water defluorinating agent and preparation method and application thereof

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