CN1257046A - High-basicity calcium type polymerized aluminium silicon chloride compound coagulant and preparation process thereof - Google Patents
High-basicity calcium type polymerized aluminium silicon chloride compound coagulant and preparation process thereof Download PDFInfo
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- CN1257046A CN1257046A CN 98123354 CN98123354A CN1257046A CN 1257046 A CN1257046 A CN 1257046A CN 98123354 CN98123354 CN 98123354 CN 98123354 A CN98123354 A CN 98123354A CN 1257046 A CN1257046 A CN 1257046A
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Abstract
The present invention relates to a new type water treatment agent-high-alkalization calcium type aluminium silicone polychloride composite coagulating agent and its preparation method. Its effective components are: Al2O3 8-12%, CaO 3-5%, SiO2 0.5-1.5% and basifier 10-90%, and its preparation method includes the following steps: under the conditions of below 100 deg.C, normal pressure and stirring, the calcium carbonate solid powder or its suspension is added to liquid aluminium polychloride by batches, then compounded with polymerized silicic acid to obtain the stable product, or firstly the aluminium polychloride and polymerized silicic acid are compounded, then the calcium carbonate is used to upward regulate its alkalinity in preparation. Said invented product possesses high functions of removing turbidity, destaining and removing fluorine, etc..
Description
The present invention relates to a kind of high-basicity calcium type polymerized aluminium silicon chloride compound coagulant and preparation technology thereof.This coagulating agent can be used for feeding water in any process and other solid-liquid separation process that needs coagulation-flocculation technology of waste water treatment engineering, is particularly useful for underground water defluorination purifying treatment.
Coagulation process is one of most widely used general, the most general unit operation technology in the engineering of water treatment.The coagulating treatment effect is directly determining the operation condition of follow-up processing flow, final outflow water quality and cost, so it is one of Technology important in the engineering of water treatment all the time.The key that obtains high-effect coagulation is the coagulating agent that must have excellent property, so coagulating agent is to use the important chemical agent that has a large capacity and a wide range in the water treatment industry.Existing very great development such as inorganic polymer coagulant polymeric aluminum, polymerization iron in the last thirty years, wherein polymerize aluminum chloride is the inorganic polymer coagulant of market sales volume maximum.Compare with traditional coagulating agent, polyaluminium coagulants can obviously improve water purification usefulness, reduces dosage, reduces cost of water treatment, improves effluent quality, has therefore obtained application more and more widely.
One of key property index of polyaluminium coagulants is a basicity.Because the high-basicity polyaluminium coagulants has stronger absorption charge neutrality, condenses and take off steady, bond bridge formation flocculation ability and conglomeration settling velocity, and regulating step has still less been avoided in the pH value reduction of processing back water.Therefore high-basicity is one of target of pursuing of polymeric aluminum production and Application Areas always.In polymerize aluminum chloride is produced, generally adopt yellow soda ash at present, sodium hydroxide, sodium aluminate, calcium aluminate breeze etc. are regulated basicity, but these methods all have certain shortcoming.Adopt yellow soda ash, sodium hydroxide is adjusted basicity and is easily produced precipitation, is difficult to obtain high-basicity and can reduces goods aluminium content, and production cost is also higher.Though adopt sodium aluminate good, need the molten preparation of aluminium hydroxide sodium aluminate of first alkali, complex process and cost are higher.Adopt the calcium aluminate breeze to dissolve under High Temperature High Pressure, energy consumption is big and solubility rate is low, and has directly influenced the polymerize aluminum chloride quality of item because foreign matter content is high.Except the basicity that improves polymerize aluminum chloride, the applicant of patent of the present invention has reported that in CN1197038A polymerize aluminum chloride and inorganic polymer polymeric silicicacid are compound, prepares the technology of polymerized aluminium silicon chloride coagulant.Polymerized aluminium silicon chloride has the coagulation-flocculation usefulness better than polymerize aluminum chloride.
The object of the invention mainly is based on the good efficiency of coagulation of polymerize aluminum chloride coagulating agent, performance is coagulated in helping that calcium salt is good, the efficient adsorption bridging ability of polymeric silicicacid, utilize solid-liquid two phase reaction reaction speed, adopt the synthetic preparation of short-cut method commercialization high-basicity calcium type polymerized aluminium silicon chloride compound coagulant.
Major technique content of the present invention is: under 0～100 ℃ of condition of normal pressure, whiting solid or its suspension liquid are joined in the polymeric aluminum chlorides solution of liquid low basicity in batches, make it acid and calcium carbonate reaction in the polymerize aluminum chloride, have carbon dioxide to emit in the reaction.For preventing that the lime carbonate conglomeration from influencing speed of response and quality product, calcium carbonate powders is uniformly distributed in the polymerize aluminum chloride, tackle reaction system for this reason and carry out vigorous stirring.This stirring also helps the release of carbon dioxide.Along with acidity in the reaction system reduces and the basicity rising, the dissolution rate of lime carbonate is slowed down, and is corresponding therewith, and the adding speed of lime carbonate should suitably be slowed down.The lime carbonate adding for the treatment of predetermined amount finishes, react completely and after not having carbon dioxide and emitting, finish to stir, obtain homogeneous, clarification, stable high-basicity calcic polymerize aluminum chloride, according to the step of preparation process of the described polymerized aluminium silicon chloride of CN1197038A (consult one of example, example two) polymeric silicicacid is incorporated in the above-mentioned high-basicity calcic polymerize aluminum chloride then, obtains homogeneous, stable, high-basicity calcium type polymerized aluminium silicon chloride efficiently.Using preparation technology of the present invention, can to obtain high-basicity be 70～90%, Al
2O
38～12%, CaO 3～5%, SiO
20.5～1.5% compound high-basicity calcium type polymerized aluminium silicon chloride coagulating agent.
Above-mentioned high-basicity calcium type polymerized aluminium silicon chloride coagulating agent also can carry out according to the following steps: earlier according to the described prepared polymerized aluminium silicon chloride of CN1197038A, add lime carbonate then and improve basicity, working method as mentioned above, finally obtain the high-basicity calcium type polymerized aluminium silicon chloride coagulating agent, experiment finds, more than two kinds of preparation process products obtained therefrom performances do not have significant difference.
The lime carbonate add-on should and preset the basicity that will reach according to original basicity, the concentration of polymerize aluminum chloride and calculate.
If existing basicity is B
1, concentration is the polymerize aluminum chloride of C (in Al mol/L), as adopts preparation technology of the present invention to reach predetermined high-basicity B
2, then should add lime carbonate amount of substance concentration and be:
[(B
2-B
1) * 3 * C] ÷ 2 and then can calculate the lime carbonate quality that will add.
The prepared high-basicity calcium type polymerized aluminium silicon chloride compound coagulant of the present invention has the flocculating settling usefulness more excellent than common polymeric aluminum, and advantage such as preparation flow is easy, and is inexpensive.Be widely used in feeding water turbidity removal, decolouring with wastewater treatment, and in other solid-liquid separation process, be particularly useful for underground drinking water defluorination purifying treatment.
One of preparation example
Measure 500mLAl
2O
315.6%, the liquid aluminium polychloride of basicity 57% takes by weighing 41.5 gram calcium carbonate powderss, the beaker that holds polymerize aluminum chloride is placed on the magnetic stirring apparatus fast stir, and divides 10 times above-mentioned calcium carbonate powders to be joined in the above-mentioned polymeric aluminum chlorides solution.Each Paris white that adds is last, should wait until to do next time after bubble that reaction system produces disappears substantially to add again.All lime carbonate added in 30 minutes, obtained the stable 500mL calcium type polyaluminium chloride of homogeneous clarification.Preparation simultaneously contains SiO
24.5% polymeric silicicacid, its pH value is 1.0, polymerization is 15 minutes in 30 degrees centigrade of water-baths.The beaker that fills 500mL calcic polymerize aluminum chloride is placed stirring fast on the magnetic stirring apparatus, the above-mentioned polymeric silicicacid of 250mL is slowly joined in the calcic polymeric aluminum chlorides solution, finally obtain 750mL homogeneous, clarifying high-basicity calcium type polymerized aluminium silicon chloride coagulating agent, the basicity 70.3% of this coagulating agent, Al concentration 2.77mol/L, Ca/Al mol ratio 0.20, Si/AlO mol ratio 0.09.
Two of preparation example
Measure 500mLAl
2O
315.6%, the liquid aluminium polychloride of basicity 57% places the beaker of 1L and is placed on the magnetic stirring apparatus and stirs fast.Preparation simultaneously contains SiO
24.5% polymeric silicicacid, its pH value is 1.0, polymerization is 15 minutes in 30 ℃ of water-baths, and this polymeric silicicacid of 250mL is slowly added in the above-mentioned polymerize aluminum chloride, obtains the clarifying polymerized aluminium silicon chloride of 750mL.Take by weighing 41.5 gram calcium carbonate powderss, it is divided join in the above-mentioned polymerized aluminium silicon chloride solution for 10 times.Each Paris white that adds is last, should wait until to do next time after bubble that reaction system produces disappears substantially to add again, and all lime carbonate added in 30 minutes, finally obtained homogeneous, clarifying 750mL high-basicity calcium type polymerized aluminium silicon chloride coagulating agent.The basicity 70.3% of this coagulating agent, Al concentration 2.77mol/L, Ca/Al mol ratio 0.20, Si/Al mol ratio 0.09.
Prepared product has satisfactory stability in the above-mentioned preparation example one and two, can not produce gelling or deposited phenomenon at least in 3 months.
In the adition process of lime carbonate, for quickening the dissolving of lime carbonate, can heat reaction system, temperature is controlled in 100 ℃.
One of application example
The coagulation turbidity removal that the high-basicity calcium type polymerized aluminium silicon chloride compound coagulant for preparing in one of above example is used for the kaolin muddy water is handled, and contrasts with polymerize aluminum chloride, polymerized aluminium silicon chloride, calcic polymerize aluminum chloride simultaneously.Raw water turbidity is 70NTU, pH value 7.55, and 17 ℃ of water temperatures, result is listed in table 1.
The high-basicity calcium type polymerized aluminium coagulation of table 1 turbidity removal effect
| Coagulating agent | Basicity | ?Ca/Al | ??Si/Al | Under the different dosages, residual turbidity (NTU) | ||
| Dosage (* 10 -5mol/L?Al 3+) | ????2.2 | ????6.6 | ????11 | |||
| Polymerize aluminum chloride | ?57％ | ?- | ??- | ????2.45 | ????0.93 | ????0.75 |
| The calcic polymerize aluminum chloride | ?70.3％ | ?0.20 | ??- | ????1.75 | ????0.75 | ????0.65 |
| Polymerized aluminium silicon chloride | ?57％ | ?- | ??0.09 | ????1.85 | ????0.86 | ????0.67 |
| Calcium type polymerized aluminium silicon chloride | ?70.3％ | ?0.20 | ??0.09 | ????1.63 | ????0.61 | ????0.49 |
From above result as seen, the coagulation turbidity removal effect of high-basicity calcium type polymerized aluminium silicon chloride compound coagulant obviously is better than former polymerize aluminum chloride, calcic polymerize aluminum chloride and polymerized aluminium silicon chloride, use the high-basicity calcium type polymerized aluminium silicon chloride compound coagulant, reach same or more excellent treatment effect, can save medicament 15～20%.
Two of application example
The coagulation turbidity removal decolouring that high-basicity calcium type polymerized aluminium silicon chloride compound coagulant prepared in one of above example is used to contain humic acids and kaolinic muddy colored water is handled, and contrasts with polymerize aluminum chloride, calcic polymerize aluminum chloride, polymerized aluminium silicon chloride simultaneously.Raw water turbidity is 18.01NTU, and colourity represents that with the absorbancy at 370nm place its value is 0.208.PH value 7.70,17 ℃ of water temperatures, result is listed in table 2.
The coagulate decoloring effect of table 2 high-basicity calcium type polymerized aluminium silicon chloride
| Coagulating agent | Basicity | ?Ca/Al | ??Si/Al | Under the different dosages, residue colourity | ||
| Dosage (* 10 -5mol/L?Al 3+) | ??2.2 | ??6.6 | ??11 | |||
| Polymerize aluminum chloride | ?57％ | ?- | ??- | ??0.089 | ??0.044 | ??0.022 |
| The calcic polymerize aluminum chloride | ?70.3％ | ?0.20 | ??- | ??0.073 | ??0.040 | ??0.019 |
| Polymerized aluminium silicon chloride | ?57％ | ?- | ??0.09 | ??0.079 | ??0.042 | ??0.019 |
| Calcium type polymerized aluminium silicon chloride | ?70.3％ | ?0.20 | ??0.09 | ??0.062 | ??0.038 | ??0.017 |
From above result as seen, the coagulation decoloration usefulness of high-basicity calcium type polymerized aluminium silicon chloride compound coagulant also is better than original polymerize aluminum chloride, calcic polymerize aluminum chloride and polymerized aluminium silicon chloride.
Three of application example
With above example two in prepared high-basicity calcium type polymerized aluminium silicon chloride compound coagulant be used for drinking water defluorination, contrast simultaneously with polymerize aluminum chloride.Former water fluorine concentration is 4mg/L.According to arts demand, add the Ca (OH) of 10g/L earlier during processing
2Solution 10mL.Stir (200 rev/mins) dispensing in the process on the coagulation experiment stirrer soon, the dispensing back was stirred 1 minute earlier soon, stirred 10 minutes (30 rev/mins) more slowly, left standstill then 10 minutes, carefully got the membrane filtration of supernatant liquor with 0.45 μ m, measured remaining fluorine concentration.The results are shown in table 3, wherein Ca/Al 0.20, Si/Al 0.09 in the calcium type polymerized aluminium silicon chloride, dosage is 50mg/LAl.
The coagulation defluorination effect of table 3 high-basicity calcium type polymerized aluminium silicon chloride
| Coagulating agent | Calcium type polymerized aluminium silicon chloride | Polymerize aluminum chloride |
| Phenomenon | Offeing medicine obvious flco occurs after 2 minutes, flocculation is fast, and flco is big | Offeing medicine obvious flco occurs after 7 minutes, flocculation is slow, and flco is little |
| Residual fluorine concentration (mg/L) | ?0.50 | ?0.80 |
Above result shows that the high-basicity calcium type polymerized aluminium silicon chloride compound coagulant is compared with corresponding polymerize aluminum chloride, has more superior defluorination performance.What is more important, when using high-basicity calcium type polymerized aluminium silicon chloride compound coagulant defluorination, its flco occurs fast, and flco is big, and sedimentation is fast.Therefore in underground water defluorination purification process technique, can significantly shorten the settling time, improve purification efficiency, help the enforcement of coagulation defluorinating process and engineering.
In sum, the high-basicity calcium type polymerized aluminium silicon chloride compound coagulant that the present invention is prepared, has better efficiency of coagulation, its preparation technology is simple and direct, product homogenisation is stable, and turbidity removal, decolouring, defluorination or other available coagulation process that prepared height alkalization calcium type polymerized aluminium silicon chloride compound coagulant can be widely used in feedwater and wastewater treatment carry out in the process of solid-liquid separation.
Claims (5)
1 one kinds of high-basicity calcium type polymerized aluminium silicon chloride compound coagulants and preparation method thereof, its effective ingredient is: Al
2O
38～12%, CaO 3～5%, SiO
20.5～1.5%, basicity is 70～90%.
2 according to claim 1, the preparation method of high-basicity calcium type polymerized aluminium silicon chloride compound coagulant, it is characterized in that, this technology is included in＜100 ℃ of normal pressures, quantitatively Powdered alkalization agent lime carbonate solid or its suspension liquid are progressively joined (the actual calcium carbonate quantity that adds should calculate according to original basicity of polymeric aluminum solution and the high-basicity value that expection obtains) in the liquid aluminium polychloride solution that hangs down basicity in batches under the intense stirring condition, obtain the calcic polymerize aluminum chloride of high-basicity after question response is complete, then polymeric silicicacid is incorporated in the calcic polymerize aluminum chloride of this high-basicity, finally obtains the high-basicity calcium type polymerized aluminium silicon chloride compound coagulant.Perhaps prepare polymerized aluminium silicon chloride earlier, heighten basicity with the lime carbonate solid again, can obtain high-basicity calcium type polymerized aluminium silicon chloride equally.
3 according to the described preparation method of claim 2, and the basicity of used polymerize aluminum chloride can be for 30～60%, concentration is the liquid product of 8.5～17% (m/m).
4 according to the described preparation method of claim 2, and basifier is for being pulverulent solids lime carbonate or its suspension liquid, and granularity is generally less than 50 orders, can solid during use or the suspension liquid form add.
The 5 high-basicity calcium type polymerized aluminium silicon chloride compound coagulants according to the described preparation of claim 1～4 are mainly used in turbidity removal, decolouring and other solid-liquid separation process of feedwater and wastewater treatment, are particularly useful for underground drinking water defluorination purifying treatment.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98123354 CN1257046A (en) | 1998-12-15 | 1998-12-15 | High-basicity calcium type polymerized aluminium silicon chloride compound coagulant and preparation process thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98123354 CN1257046A (en) | 1998-12-15 | 1998-12-15 | High-basicity calcium type polymerized aluminium silicon chloride compound coagulant and preparation process thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348510C (en) * | 2005-06-06 | 2007-11-14 | 山东大学 | Preparation of polyaluminum chloride coagulant with high Alb content by solid-solid compounding process |
| CN103232079A (en) * | 2012-06-01 | 2013-08-07 | 深圳市东港城投资有限公司 | Formula and preparation method of natural mineral dyeing and printing industry wastewater treatment agent |
| CN104609697A (en) * | 2015-02-28 | 2015-05-13 | 西安市利生污泥处理有限公司 | Composite sludge gel breaker as well as preparation and application thereof |
| EP3437707A4 (en) * | 2016-03-31 | 2019-10-23 | Kurita Water Industries Ltd. | Agent for treating wet-coating-booth circulation water and method for treating wet-coating-booth circulation water |
| CN113955873A (en) * | 2021-09-23 | 2022-01-21 | 鄂尔多斯市紫荆创新研究院 | Water treatment defluorinating agent suitable for micro-polluted raw water and preparation and use methods thereof |
-
1998
- 1998-12-15 CN CN 98123354 patent/CN1257046A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348510C (en) * | 2005-06-06 | 2007-11-14 | 山东大学 | Preparation of polyaluminum chloride coagulant with high Alb content by solid-solid compounding process |
| CN103232079A (en) * | 2012-06-01 | 2013-08-07 | 深圳市东港城投资有限公司 | Formula and preparation method of natural mineral dyeing and printing industry wastewater treatment agent |
| CN103232079B (en) * | 2012-06-01 | 2015-02-11 | 邱兵 | Formula and preparation method of natural mineral dyeing and printing industry wastewater treatment agent |
| CN104609697A (en) * | 2015-02-28 | 2015-05-13 | 西安市利生污泥处理有限公司 | Composite sludge gel breaker as well as preparation and application thereof |
| EP3437707A4 (en) * | 2016-03-31 | 2019-10-23 | Kurita Water Industries Ltd. | Agent for treating wet-coating-booth circulation water and method for treating wet-coating-booth circulation water |
| US10745302B2 (en) | 2016-03-31 | 2020-08-18 | Kurita Water Industries Ltd. | Method for treating water that circulates through wet paint booth |
| CN113955873A (en) * | 2021-09-23 | 2022-01-21 | 鄂尔多斯市紫荆创新研究院 | Water treatment defluorinating agent suitable for micro-polluted raw water and preparation and use methods thereof |
| CN113955873B (en) * | 2021-09-23 | 2023-08-29 | 鄂尔多斯市紫荆创新研究院 | Water treatment defluorinating agent suitable for micro-polluted raw water and preparation and use methods thereof |
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