CN103922513A - Method for removing sulfate in water by generating compound precipitation with aluminium salt as crystal nucleus - Google Patents
Method for removing sulfate in water by generating compound precipitation with aluminium salt as crystal nucleus Download PDFInfo
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- CN103922513A CN103922513A CN201410186417.1A CN201410186417A CN103922513A CN 103922513 A CN103922513 A CN 103922513A CN 201410186417 A CN201410186417 A CN 201410186417A CN 103922513 A CN103922513 A CN 103922513A
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- water
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- vitriol
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Abstract
The invention relates to a method for removing sulfate in water, and in particular relates to a method for removing sulfate in water by generating compound precipitation with aluminium salt as a crystal nucleus, aiming at solving the technical problems that the existing method for removing the sulfate is high in cost and complicated. The method comprises the steps of firstly feeding the aluminium salt into the water, then feeding calcium salt into the water, and stirring to obtain mixer a; feeding quick lime or lime milk suspension into the mixer a, stirring and standing still; carrying out solid-liquid separation, and adjusting the pH value. According to the method, the aluminium salt is taken as the crystal nucleus and is combined with calcium ions and sulfate ions under the alkaline condition, so that the compound Can Al2m (SO4)3x (OH)12.zH2O which is insoluble in water can be generated. The aluminium chloride, calcium chloride and quick lime which are selected by the method have the characteristics of wide source and low price, so that the running cost is low when the method is used for treating the water with excessive sulfate. The method belongs to the field of water treatment.
Description
Technical field
The present invention relates to a kind of method of removing vitriol in water.
Background technology
Along with the fast development of China's economy, the problems such as environmental pollution, environmental disruption, environmental degradation are more and more serious.Statistical information shows that the surface water and groundwater water quality in many rivers, lake and city worsens increasingly, and Drinking Water for Residents source is subject to serious pollution threat.In surface water, underground water, drinking water source, to exceed standard be present a kind of common water pollution problems to vitriol.In water, vitriol exceeds standard and can destroy water ecological environment, the growth of harm hydrobiont; Long-term drinking is prone to the disease such as diarrhoea, intestinal function disorder; In agricultural, use the vitriol water body irrigation meeting spoiled soil structure that exceeds standard, form saltings, suppress crop growth.In industrial production, use the vitriol water body that exceeds standard can cause hydrophone fouling, corrosion pipeline and production unit, form higher potential safety hazard.
At present, the method for common removal vitriol has, barium chloride method, calcium method, ion exchange method, SRS embrane method, absorption method, biological process etc.Barium chloride method technique is skillful, flow process is short, clearance can reach more than 97%, can obtain by product barium sulfate; But bariumchloride price is high, increase running cost, excessive bariumchloride is poisonous, and not environmental protection easily causes former water secondary pollution.The principle that calcium method is removed sulfate radical is that calcium ion can generate calcium sulfate precipitation (CaSO with sulfate ion association reaction under certain condition
42H
2o),, after solid-liquid separation, the form that sulfate radical can gypsum is removed.Calcium method running cost is low, can obtain by product gypsum, but calcium sulfate solubleness is large, (solubility product 25 DEG C time is 7.1 × 10
-5), removal efficiency is low, and technical requirements complexity, goes out alkalinity of water high, and therefore the scope of application of this method is little.Ion exchange method technique is skillful, exchange velocity is fast, selectivity is strong, removal efficiency is high, material reusable edible, use in extensive rangely, but that pre-treatment requires is strict, facility investment is higher.SRS embrane method is a kind of nanofiltration technology, has that selectivity is strong, clearance is high, simple to operate, the advantage such as working cost is low, investment repayment is fast, but cost is high, is more difficult to realize extensive operation.Absorption method raw material preparation cost is low, pollutes littlely, is the good vitriol of development prospect removal method; But adsorption mechanism is indefinite, absorption property is unstable, at present also in the laboratory study stage.Biological process is applicable to processing and is rich in the water body of organism and vitriol simultaneously, but easily introduces impurity, causes secondary pollution.
Summary of the invention
The object of the invention is the technical problem that method cost is high, method is complicated in order to solve existing removal vitriol, a kind of method of making vitriol in nucleus generation mixture precipitation removal water with aluminium salt is provided.
Make the method for vitriol in nucleus generation mixture precipitation removal water carries out according to following steps with aluminium salt:
One, Xiang Shuizhong adds aluminium salt and calcium salt, is stirred to completely and dissolves, and obtains mixture a, and wherein the mol ratio of aluminium salt and calcium salt is 1.0～1.2 ﹕ 1.0, and in mixture a, the concentration of aluminum ion and calcium ion is respectively 0.1～0.15g/L and 0.144～0.234g/L;
Two, in mixture a, add unslaked lime or milk of lime suspension liquid, the mol ratio of calcium salt described in unslaked lime or milk of lime suspension liquid and step 1 is 1.4～1.6 ﹕ 1.0, stirring velocity with 100r/min stirs 20～30 minutes, now the pH value of mixed solution is 11.0～12.0, leave standstill 15-20 minute, carry out solid-liquid separation;
Three, the clear liquid of solid-liquid separation in step 2 is regulated to pH value to 7.0～8.5 by acid solution, complete the process of making vitriol in nucleus generation mixture precipitation removal water with aluminium salt.
Aluminium salt described in step 1 is a kind of in aluminum chloride, aluminum nitrate, polymerize aluminum chloride and polymerization aluminum nitrate or several mixture wherein.
Calcium salt described in step 1 is one or both the mixture in calcium chloride and nitrocalcite.
In step 2, the mode of solid-liquid separation is normal pressure filtration, gravity filtration or through bottom bucket spoil disposal.
Acid solution described in step 3 is hydrochloric acid.
The present invention has following beneficial effect:
1) the present invention makes nucleus with aluminium salt, is combined generates mixture Ca not soluble in water under alkaline condition with calcium ion, sulfate ion
nal
2m(SO
4)
3x(OH)
12zH
2o.
2) the selected medicament aluminum chloride of the present invention, calcium chloride, unslaked lime all have wide material sources, cheap feature, make to adopt this kind of method to process the exceed standard running cost of water body of vitriol low.
3) the inventive method processing efficiency high, pollute little, method is simple, investment repayment is fast, is applicable to various water bodys, easily realizes extensive operation.
After adopting the inventive method to process, in water, sulphate content is less than 250mg/L, meets " drinking water sanitary standard " (GB5749-2006).
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the method that present embodiment is made vitriol in nucleus generation mixture precipitation removal water with aluminium salt is carried out according to following steps:
One, Xiang Shuizhong adds aluminium salt and calcium salt, is stirred to completely and dissolves, and obtains mixture a, and wherein the mol ratio of aluminium salt and calcium salt is 1.0～1.2 ﹕ 1.0, and in mixture a, the concentration of aluminum ion and calcium ion is respectively 0.1～0.15g/L and 0.144～0.234g/L;
Two, in mixture a, add unslaked lime or milk of lime suspension liquid, the mol ratio of calcium salt described in unslaked lime or milk of lime suspension liquid and step 1 is 1.4～1.6 ﹕ 1.0, stirring velocity with 100r/min stirs 20～30 minutes, now the pH value of mixed solution is 11.0～12.0, leave standstill 15-20 minute, carry out solid-liquid separation;
Three, the clear liquid of solid-liquid separation in step 2 is regulated to pH value to 7.0～8.5 by acid solution, complete the process of making vitriol in nucleus generation mixture precipitation removal water with aluminium salt.
After adopting present embodiment to process, in water, sulphate content is less than 250mg/L, meets " drinking water sanitary standard " (GB5749-2006).
Embodiment two: what present embodiment was different from embodiment one the is aluminium salt described in step 1 is in aluminum chloride, aluminum nitrate, polymerize aluminum chloride and polymerization aluminum nitrate a kind of or several mixture wherein.Other is identical with embodiment one.
Embodiment three: what present embodiment was different from one of embodiment one or two the is calcium salt described in step 1 is in calcium chloride and nitrocalcite one or both mixture.Other is identical with embodiment one or two.
Embodiment four: what present embodiment was different from one of embodiment one to three is that the acid solution described in step 3 is hydrochloric acid.Other is identical with one of embodiment one to three.
Embodiment five: the mol ratio of what present embodiment was different from one of embodiment one to four is in step 1 aluminium salt and calcium salt is 1.1 ﹕ 1.0.Other is identical with one of embodiment one to four.
Embodiment six: the mol ratio of what present embodiment was different from one of embodiment one to five is in step 2 calcium salt described in unslaked lime or milk of lime suspension liquid and step 1 is 1.5 ﹕ 1.0.Other is identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different from one of embodiment one to six is that in step 2, churning time is 25 minutes.Other is identical with one of embodiment one to six.
Embodiment eight: the mode of solid-liquid separation in step 2 that what present embodiment was different from one of embodiment one to seven is is normal pressure filtration, gravity filtration or through bottom bucket spoil disposal.Other is identical with one of embodiment one to seven.
Embodiment nine: what present embodiment was different from one of embodiment one to eight is to regulate pH value to 8.0 by acid solution in step 3.Other is identical with one of embodiment one to eight.
Adopt following experimental verification effect of the present invention:
Experiment one:
The source water 1000mL of Qu Mou water factory, before processing, in water, sulphate content is 500mg/L, in water sample, adds 0.50gAlCl
36H
2o, 0.57gCaCl
26H
2o, 0.90gCaO, normal temperature was with the speed stirring reaction of 100r/min 30 minutes, standing sedimentation 20 minutes, solid-liquid separation, regulating clear liquid pH value is 7.0-8.5, in clear liquid, sulphate content is 66.55mg/L by analysis, and the clearance that calculates Sulfate in Water is 86.69%.
Experiment two:
Get somewhere underground water 1000mL, before processing, in water, sulphate content is 600mg/L, and Xiang Shuizhong adds 0.55g/LAlCl
36H
2o, 0.57g/LCaCl
26H
2o, 1.00gCaO, normal temperature was with the speed stirring reaction of 100r/min 30 minutes, standing sedimentation 20 minutes, solid-liquid separation, regulates clear liquid pH value 7.0-8.5, in clear liquid, sulphate content is 70.86mg/L by analysis, and the clearance that calculates Sulfate in Water is 88.19%.
Experiment three:
Get certain trade effluent 1000mL, before processing, in water, sulphate content is 1100mg/L, and Xiang Shuizhong adds 0.84g/LAlCl
36H
2o, 0.72g/LCaCl
26H
2o, 1.30gCaO, normal temperature was with the speed stirring reaction of 100r/min 30 minutes, standing sedimentation 20 minutes, solid-liquid separation, regulates clear liquid pH=7.0-8.5, in clear liquid, sulphate content is 106.92mg/L by analysis, and the clearance that calculates Sulfate in Water is 90.28%.
Claims (9)
1. make nucleus and generate mixture precipitation and remove the method for vitriol in water with aluminium salt, it is characterized in that making nucleus with aluminium salt generates mixture precipitation and remove the method for vitriol in water and carry out according to following steps:
One, Xiang Shuizhong adds aluminium salt and calcium salt, is stirred to completely and dissolves, and obtains mixture a, and wherein the mol ratio of aluminium salt and calcium salt is 1.0～1.2 ﹕ 1.0, and in mixture a, the concentration of aluminum ion and calcium ion is respectively 0.1～0.15g/L and 0.144～0.234g/L;
Two, in mixture a, add unslaked lime or milk of lime suspension liquid, the mol ratio of calcium salt described in unslaked lime or milk of lime suspension liquid and step 1 is 1.4～1.6 ﹕ 1.0, stirring velocity with 100r/min stirs 20～30 minutes, now the pH value of mixed solution is 11.0～12.0, leave standstill 15-20 minute, carry out solid-liquid separation;
Three, the clear liquid of solid-liquid separation in step 2 is regulated to pH value to 7.0～8.5 by acid solution, complete the process of making vitriol in nucleus generation mixture precipitation removal water with aluminium salt.
2. make nucleus and generate mixture precipitation and remove according to claim 1 the method for vitriol in water with aluminium salt, it is characterized in that the aluminium salt described in step 1 is a kind of in aluminum chloride, aluminum nitrate, polymerize aluminum chloride and polymerization aluminum nitrate or several mixture wherein.
3. make nucleus and generate mixture precipitation and remove according to claim 1 the method for vitriol in water with aluminium salt, it is characterized in that the calcium salt described in step 1 is one or both the mixture in calcium chloride and nitrocalcite.
4. the method for making according to claim 1 vitriol in nucleus generation mixture precipitation removal water with aluminium salt, is characterized in that the acid solution described in step 3 is hydrochloric acid.
5. according to the method for making nucleus and generate mixture precipitation and remove vitriol in water described in claim 1,2,3 or 4 with aluminium salt, it is characterized in that in step 1, the mol ratio of aluminium salt and calcium salt is 1.1 ﹕ 1.0.
6. according to the method for making nucleus and generate mixture precipitation and remove vitriol in water described in claim 1,2,3 or 4 with aluminium salt, it is characterized in that the mol ratio of calcium salt described in unslaked lime in step 2 or milk of lime suspension liquid and step 1 is 1.5 ﹕ 1.0.
7. according to the method for making vitriol in nucleus generation mixture precipitation removal water described in claim 1,2,3 or 4 with aluminium salt, it is characterized in that in step 2, churning time is 25 minutes.
8. according to the method for making nucleus and generate mixture precipitation and remove vitriol in water described in claim 1,2,3 or 4 with aluminium salt, the mode that it is characterized in that solid-liquid separation in step 2 is normal pressure filtration, gravity filtration or through bottom bucket spoil disposal.
9. according to the method for making vitriol in nucleus generation mixture precipitation removal water described in claim 1,2,3 or 4 with aluminium salt, it is characterized in that regulating pH value to 8.0 by acid solution in step 3.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410186417.1A CN103922513A (en) | 2014-05-05 | 2014-05-05 | Method for removing sulfate in water by generating compound precipitation with aluminium salt as crystal nucleus |
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| CN201410186417.1A CN103922513A (en) | 2014-05-05 | 2014-05-05 | Method for removing sulfate in water by generating compound precipitation with aluminium salt as crystal nucleus |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114275959A (en) * | 2021-12-29 | 2022-04-05 | 吉林省拓达环保设备工程有限公司 | Agent for removing high-concentration sulfate and nitrate in water and removing method and device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070209989A1 (en) * | 2004-04-26 | 2007-09-13 | Mitsubishi Materials Corporation | Reducing water purification material, method for producing reducing water purification material, method for treating wastewater, and wastewater treatment apparatus |
| CN101407356A (en) * | 2008-10-31 | 2009-04-15 | 中南大学 | Method for removing sulfate radical in waste water |
| CN102674515A (en) * | 2012-05-18 | 2012-09-19 | 上海大学 | Method for regulating, controlling and forming hydrotalcite-like compound deep treatment leachate tail water |
-
2014
- 2014-05-05 CN CN201410186417.1A patent/CN103922513A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070209989A1 (en) * | 2004-04-26 | 2007-09-13 | Mitsubishi Materials Corporation | Reducing water purification material, method for producing reducing water purification material, method for treating wastewater, and wastewater treatment apparatus |
| CN101407356A (en) * | 2008-10-31 | 2009-04-15 | 中南大学 | Method for removing sulfate radical in waste water |
| CN102674515A (en) * | 2012-05-18 | 2012-09-19 | 上海大学 | Method for regulating, controlling and forming hydrotalcite-like compound deep treatment leachate tail water |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114275959A (en) * | 2021-12-29 | 2022-04-05 | 吉林省拓达环保设备工程有限公司 | Agent for removing high-concentration sulfate and nitrate in water and removing method and device |
| CN114275959B (en) * | 2021-12-29 | 2023-12-01 | 吉林省拓达环保设备工程有限公司 | Medicament for removing high-concentration sulfate and nitrate in water and removing method and device |
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Application publication date: 20140716 |