CN101402481A - Mesoporous adsorption type aluminum salt composite flocculent synthesis method and uses thereof - Google Patents
Mesoporous adsorption type aluminum salt composite flocculent synthesis method and uses thereof Download PDFInfo
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- CN101402481A CN101402481A CNA2008102012722A CN200810201272A CN101402481A CN 101402481 A CN101402481 A CN 101402481A CN A2008102012722 A CNA2008102012722 A CN A2008102012722A CN 200810201272 A CN200810201272 A CN 200810201272A CN 101402481 A CN101402481 A CN 101402481A
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Abstract
The invention belongs to the technical field of chemical engineering and environment, and in particular relates to a method for synthesizing a mesoporous adsorption type aluminum salt composite coagulant and application thereof. The method comprises the following steps: at the room temperature, mixing evenly the solid materials of calcium aluminate and calcium hydroxide or calcium oxide, and grinding and crushing the solid materials till the grain diameter is less than 200 meshes so as to form a component A; and mixing evenly silicon dioxide and solid polyaluminium chloride, and grinding and crushing the silicon dioxide and the solid polyaluminium chloride till the grain diameter is less than 200 meshes so as to form a component B. The mass ratio of the calcium aluminate to the calcium hydroxide or the calcium oxide is 1:0.1 to 1:0.2; the mass ratio of the polyaluminium chloride to the silicon dioxide is 1:1.5 to 1: 0.1; and during the use, and the dosage ratio of the component A to the component B is 1:0.1 to 1:0.01. The component A and the component B are added into a water body containing anion nitrates or nitrites respectively, the water body is stirred for 5 to 10 minutes, and the removal rate of the nitrate or nitrite ions in the solution can reach 90 to 99.9 percent. The method has the advantages of simplicity, easily obtained raw materials, low cost and very good effects on treating the water and waste water containing the nitrate and nitrite ions, broad development value and application prospect.
Description
Technical field
The invention belongs to chemical industry and environmental technology field, be specifically related to a kind of mesoporous adsorption type aluminum salt composite flocculent synthesis method and and application.
Background technology
Serious day by day along with industrial pollution developed and uses new and effective sorbent material and coagulating agent more and more to cause people's attention.Mesoporous material is the new adsorbent of a kind of aperture in the 2-50 nanometer, the organic and inorganic pollutant in can the active adsorption water body, and mesoporous material commonly used comprises aluminum oxide, silicon oxide molecular sieve, natural shape clay etc.The synthetic mesoporous material has pore size distribution functional mesoporous sorbing material narrow, stable in properties, becomes domestic and international many research focuses.The SiO 2 mesoporous materials that forms of tetraethyl-silica alkane hydrolysis for example, by β-aminopropyl-triethoxy siloxanes or after β-the sulfydryl propyl-triethoxysilicane is siloxane modified, make mesoporous material surface amination or sulfhydrylation, make it to give the function of heavy metal cation in the complexing water body.If the mesoporous material surface covers for positively charged ion, for example sodium ion, calcium ion, magnesium ion etc. then further with in the water body have the form that negatively charged ion forms insoluble metallic salt in treating processes, then possess the happy anionic function of water body weight of removing.
Coagulating agent is the chemical agent that a kind of efficient removal causes the tiny suspended particle that water pollutes, and can take off steady and cohesion by colloidal, fine particle is become be easy to isolating flco, thereby be easy to from water body weight by natural subsidence or pneumatically supported mode from coming out.Coagulating agent principal item polymerize aluminum chloride and the bodied ferric sulfate that widely uses, and the Tai-Ace S 150 of low-molecular inorganic at present.China's research inorganic polymer coagulant polymerize aluminum chloride has had the history in more than 30 year, but the effect of polymerize aluminum chloride is unsatisfactory aspect the negatively charged ion in removing water body, especially for the bigger waste water of saltiness, for example nitrate, vitriol, hydrochloride etc.There is not clear and definite standard for saltiness than the present country of higher waste water, but often cause salting of soil after the high slat-containing wastewater discharging, soil compaction, forfeiture fertility and plantation function, along with China for the tightening up day by day of sewage discharge index, will face bigger blowdown presssure for the saltiness of sewage.But polymerize aluminum chloride is being one of at present best coagulating agent aspect the removal colloid, and especially its bridge formation ability is more outstanding.Do not have strict requirement for polymerize aluminum chloride in this patent, its basicity is in 30% to 95% scope, and what alumina content can be in order to silicon-dioxide in 20% to 35% scope is compound, and does not influence its result of use.
The nitrogenous effluent that discharges in the Industrial processes, the nitrogenous fertilizer of using on the agricultural becomes the source of rivers and lakes eutrophication maximum, enter receiving water body after, ammonia nitrogen organonitrogen etc. can change into nitrate radical (NO
3 -) or nitrite anions (NO
3 -).After nitrate radical enters human body, be reduced to nitrite anions, and become carcinogenic substance.Therefore the nitrate in the water body and the removal of nitrite become urgent problem.
Above-mentioned novel adsorptive type coagulating agent utilize coagulating agent in precipitation process with water body in negatively charged ion form coprecipitate [Ca (AlO
2)
2]
x[CaSiO
3]
y[Ca (NO
3)
2)]
yXH
2O and [Ca (AlO
2)
2]
x[CaSiO
3]
y[Ca (NO
2)
2)]
yXH
2The principle of O can effectively be removed nitrate and nitrite plasma in the water body, reaches the purpose of removal.This method also can be removed the total nitrogen that mainly exists with nitrate and nitrite form in the water body simultaneously.Owing to contain a certain amount of polymerize aluminum chloride in the compound coagulant, so it has the multiple function of absorption, precipitation and cohesion, and the organic efficient in the removal water body is higher.
Adsorption type aluminum salt composite flocculent belongs to inorganic polymer coagulant, many advantages are arranged, as removing fine dispersion state particulate matter and some negatively charged ion that some conventional coagulating agent can't be removed, nitrate radical for example, nitrite anions, sulfate radical, chlorion etc., and the alumen ustum that generates in the water purification process is bigger, the intensity height, settling velocity is fast, when sewage disposal to some heavy metal ion, copper for example, plumbous plasma and COD, colourity, stenches etc. all have significant removal effect, to treating water pH value wide accommodation (pH=4-11), especially the treatment effect of municipal wastewater and trade effluent is better.
Summary of the invention
Order of the present invention be to propose a kind of effective, cost is low, the mesoporous adsorption type aluminum salt composite flocculent synthesis method of good stability and application thereof.
The mesoporous adsorption type aluminum salt composite flocculent production method that the present invention proposes, concrete steps are: at ambient temperature, solid material calcium aluminate and calcium hydroxide or calcium oxide are mixed, grind to particle diameter below 200 orders, form component A; Silicon-dioxide and solid polyaluminium chloride are mixed, grind to 200 orders, form B component; Wherein, the mass ratio of calcium aluminate and calcium hydroxide or calcium oxide is 1: 0.1-1: 0.2, and the mass ratio of polymerize aluminum chloride and silicon-dioxide is 1: 1.5-1: 0.1, during use, component A is 1 with the ratio of the dosage of B component: 0.1-1: 0.01.
Among the present invention, calcium aluminate powder can be to produce polymerize aluminum chloride calcium aluminate commonly used, and its alumina content is at 40-60%, and calcium oxide content is between 20-35%.Its specific surface area is greater than 50.0m
2/ g, mean pore size is 5-8nm.Grain diameter is generally the smaller the better, just can reach extraordinary absorption and sedimentation effect at particle during less than 200 orders.There is not specific requirement for calcium hydroxide or lime herein.
Among the present invention, the particle diameter of silicon-dioxide is below 200 orders.
Product index of the present invention is: component A: specific surface area: 20-50m
2/ g; Mean pore size: 11-15nm; B component: water soluble oxidized aluminium content: 3-15%.
Utilize the application in nitrate ion or the nitrite ion in removing solution of compound coagulant that the inventive method prepares.Concrete steps are: add component A and B respectively in the water body that contains negatively charged ion nitrate radical or nitrite anions, stirred 5-10 minute, then nitrate radical or nitrite ion clearance reach 90-99,9% in the solution.
The mesoporous adsorption type aluminum salt composite flocculent of the present invention's preparation has the triple role of physical adsorption, co-precipitation and chemical flocculation in the process of water treatment, solid particles surface has formed the hole and the hole of many mesoporous sizes on the one hand, the organism in the energy active adsorption water body; On the other hand, because calcium aluminate, calcium hydroxide and nitrate or nitrite can form the co-precipitation insolubles, effectively remove the negatively charged ion in the solution; Moreover, from water body, separate rapidly because the coagulation that polymerize aluminum chloride and superfine silicon dioxide mixture utilize polymerize aluminum chloride further takes off the insolubles of above-mentioned formation surely, condenses, forms big particulate matter.Silicon-dioxide in polymerize aluminum chloride and the silica composite has further been strengthened absorption and flocculation process again in addition, make the easier sedimentation of flco with separate.
Above-mentioned these multiple co-precipitation-absorption-coagulations are actual has strengthened conventional coagulation process, organic pollutant and anionic effect in the removal water body have been reached, thereby form the more aggregate of macromolecule, in absorption and bridge formation flocculation process, can greater advantages bring into play macromolecular flocculating effect.Therefore suspended particle, some heavy metal ion and COD, colourity, stench etc. all there are significant removal effect, especially better for anionic removal effect.Flco forms speed is fast, alumen ustum is closely knit, settling velocity is fast characteristic, and can to have overcome the flco that adopts conventional polymerize aluminum chloride etc. often to form fully light, is not easy precipitation, removes the inefficient shortcoming of negatively charged ion.
The present invention adopts compound production solid mesoporous adsorption type aluminum salt composite flocculent, the preparation method is simple, raw material is easy to get, cost is low, in use can use according to the mode that A, B component are added to respectively in the pending water, it is easy to operate, removes negatively charged ion, Organic pollutants water is effective, has extraordinary using value.
Description of drawings
Fig. 1 is that the embodiment of the invention 1 is removed nitrite anions coagulation experiment result.
Fig. 2 is that the embodiment of the invention 2 is removed nitrate radical coagulation experiment result.
Embodiment
Embodiment 1: at ambient temperature, add 500g calcium aluminate and 50 gram calcium hydroxides in ball mill.The calcium aluminate index is as follows: alumina content: 52.4%, and calcium oxide content: 29.4%, iron oxide content: 2.4%.Calcium hydroxide content: greater than 90%.At room temperature ball milling is 4 hours, then sample is taken out, and it is component A that mistake 200 mesh sieves obtain sample.This product index is as follows: specific surface area: 97.8m
2/ g; Mean pore size: 13.5nm.
With industrial simulated sewage is former water, carries out coagulation experiment with the mesoporous Al adsorption salt composite flocculent of the solid of method for preparing.The processing volume of water sample is 100ml, and the concentration of Sodium Nitrite is 0.1mol/L.Add 100ml solution respectively in 5 beakers, add A component coagulating agent 1,2,5 then respectively, 10g stirs 30s fast under 300 rev/mins of speed, add coagulating agent B component 0.2g then, stirs 30s fast, stirs static 5 minutes then at a slow speed 10 minutes.Measure nitrite content in the supernatant liquor.The results are shown in Table 1 and Fig. 1.
Table 1 coagulation experiment result
| Coagulating |
0 | 1 | 2 | 5 | 10 |
| Dosage (g) | |||||
| Concentration (mol/L) | 0.1 | 0.0026 | 0.00075 | 0.000175 | 0.000005 |
Embodiment 2: at ambient temperature, add 250g polymerize aluminum chloride and 250 gram superfine silicon dioxides in ball mill.The index of polymerize aluminum chloride is as follows: alumina content: 28.4%, and basicity: 92.4%, iron oxide content: 0.7%, insolubles content: 1.1%.Calcium hydroxide content: greater than 90%.At room temperature ball milling is 1 hour, then sample is taken out, and it is B component that mistake 100 mesh sieves obtain sample.The index of product B is as follows according to standard GB 15892-2003 testing index: aluminum oxide 14.0%, basicity: 47.2%.
To dilute back nitric acid acidwashing waste liquid is former water (nitrate concentration is 0.1mol/L), and the mesoporous Al adsorption salt composite flocculent of solid for preparing with preceding method carries out coagulation experiment.In 5 beakers, add 500ml solution respectively, add coagulating agent A:0 respectively, 0.5,1.0,1.5,2.0,2.5,3.0g/L.Behind the dosing coagulant A, at first stirred 30 seconds, add coagulating agent B component 100mg then, stirred 10 minutes at 50 rev/mins then, after static again 20 minutes, get supernatant liquor, determine nitrate by the beaker middle part at 300 rev/mins.Result is seen specification sheets table 2 and Fig. 2.
Table 2 coagulation experiment result
| Coagulating agent component A dosage (g/L) | 0 | 0.5 | 1.0 | 1.5 | 2.0 | 2.5 | 3.0 |
| Concentration (mol/L) | 0.1 | 0.000125 | 0.00025 | 0.000375 | 0.00011 | 0.00001 | 0.00001 |
Claims (2)
1, a kind of mesoporous adsorption type aluminum salt composite flocculent production method is characterized in that concrete steps are: at ambient temperature, solid material calcium aluminate and calcium hydroxide or calcium oxide are mixed, grind to particle diameter below 200 orders, form component A; Silicon-dioxide and solid polyaluminium chloride are mixed, grind to 200 orders, form B component; Wherein, the mass ratio of calcium aluminate and calcium hydroxide or calcium oxide is 1: 0.1-1: 0.2, and the mass ratio of polymerize aluminum chloride and silicon-dioxide is 1: 1.5-1: 0.1, during use, component A is 1 with the ratio of the dosage of B component: 0.1-1: 0.01.
2, the compound coagulant for preparing of a kind of method according to claim 1 application in nitrate ion or the nitrite ion in removing solution.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206001A (en) * | 2011-04-29 | 2011-10-05 | 同济大学 | Composite decolorizer as well as preparation method and application thereof |
| CN103979655A (en) * | 2013-11-01 | 2014-08-13 | 季红军 | Sewage treatment agent and preparation method thereof |
| CN104888715A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Modified volcanic rock adsorbent for processing waste water |
| CN104888714A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Modified volcanic rock adsorbent microsphere |
| CN104888713A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Volcanic rock adsorbent for flue gas mercury removal and preparation method of volcanic rock adsorbent |
| CN104888698A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Adsorbent capable of adsorbing gasoline steam |
| CN104888699A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Modified volcanic rock dedusting adsorbent |
-
2008
- 2008-10-16 CN CNA2008102012722A patent/CN101402481A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206001A (en) * | 2011-04-29 | 2011-10-05 | 同济大学 | Composite decolorizer as well as preparation method and application thereof |
| CN103979655A (en) * | 2013-11-01 | 2014-08-13 | 季红军 | Sewage treatment agent and preparation method thereof |
| CN103979655B (en) * | 2013-11-01 | 2015-08-26 | 浙江省农业科学院 | A kind of sewage treatment drug and preparation method thereof |
| CN104888715A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Modified volcanic rock adsorbent for processing waste water |
| CN104888714A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Modified volcanic rock adsorbent microsphere |
| CN104888713A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Volcanic rock adsorbent for flue gas mercury removal and preparation method of volcanic rock adsorbent |
| CN104888698A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Adsorbent capable of adsorbing gasoline steam |
| CN104888699A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Modified volcanic rock dedusting adsorbent |
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Open date: 20090408 |