CN100412001C - Acidic waste water treatment agent capable of regenerative cycle use and preparation method thereof - Google Patents

Acidic waste water treatment agent capable of regenerative cycle use and preparation method thereof Download PDF

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CN100412001C
CN100412001C CNB2006101407538A CN200610140753A CN100412001C CN 100412001 C CN100412001 C CN 100412001C CN B2006101407538 A CNB2006101407538 A CN B2006101407538A CN 200610140753 A CN200610140753 A CN 200610140753A CN 100412001 C CN100412001 C CN 100412001C
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waste water
treatment agent
hydrotalcite
acid waste
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CN1919748A (en
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赵芸
矫庆泽
刘睿
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Beijing Institute of Technology BIT
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Abstract

The invention discloses a renewable industrial acid waste water disposing agent and preparing method, which is characterized by the following: adopting magnesium hydrotalcite as former; sintering to obtain the magnesium composite metal oxide; adopting hydrotalcite material structure to dispose acid waste water.

Description

A kind of renewable acidic waste water treatment agent that recycles
Technical field
The present invention relates to a kind of renewable treatment agent that recycles that is used for industrial acidic wastewater, belong to the environmental protection field.
Background technology
Industries such as mining ore dressing, chemical industry, pharmacy, metallurgy can produce a large amount of acid waste water.In the prior art, the treatment process of industrial acidic wastewater comprises sulphate reducing bacteria method, active carbon adsorption and coagulant sedimentation, catalytic oxidation and wet oxidation process, lime neutralization precipitation facture etc.Agent is a kind of method of the most widely using as neutralizing treatment wherein to adopt Wingdale cheap and easy to get and lime.Yet there are shortcomings such as consumption is big, labor condition is poor, effect is undesirable in lime neutralization precipitation facture.
CN86106532A provides a kind of acidic waste water treatment agent of being made up of alkaline inorganic compound, high polymer binder and water, and its alkaline inorganic compound is selected from lime, Wingdale, white lime, magnesium oxide, magnesium hydroxide or its mixture.Exist treatment agent to be difficult to regenerate, can cause the shortcoming of secondary pollution.
It is effective constituent with the inorganic salt in the industrial acidic wastewater waste liquid that CN02148522.4 provides a kind of, by adding carbonatite or Calcareous material or containing solution of caustic soda etc., preparation can be used for the hydrotalcite product in fields such as waste water drinking water treatment when handling waste water and waste liquid, shortcoming is a complex process, need to detect the content of metal ion in the waste water and in waste water, add an amount of metal ion, so that the ratio of divalence and trivalent metal ion is suitable in the reactor.
Summary of the invention
The purpose of this invention is to provide a kind of renewable acidic waste water treatment agent that recycles, this treatment agent is to be the Al-Mg composite metal oxide that precursor obtains through roasting with the magnesium aluminum-hydrotalcite, and it has the crystalline structure similar to magnesium oxide, and its composition general formula is:
Mg 1-xAl xO (OH) x, wherein the magnalium mol ratio can be from 1.6: 1--10: 1
Utilize the structure memory effect to reach the purpose of treatment of acidic wastewater.
The preparation technology of acidic waste water treatment agent of the present invention----Al-Mg composite metal oxide is as follows: at first adopt coprecipitation method to prepare magnesium aluminum-hydrotalcite, and then obtain Al-Mg composite metal oxide in 430-700 ℃ of roasting.Concrete steps are: the preparation of A. salts solution: solubility magnesium salts and aluminium salt is soluble in water, be mixed with mixing salt solution, and described magnesium salts and aluminium salt are nitrate, vitriol or hydrochloride, wherein [Mg 2+] concentration be 0.1-4.0mol/L, [Al 3+] concentration is 0.05-2.0mol/L, [Mg 2+]/[Al 3+] mol ratio is 1.6: 1--10: 1; B. alkaline solution preparation: with the water-soluble alkaline solution that is mixed with of sodium hydroxide, yellow soda ash, ammoniacal liquor, volatile salt, potassium hydroxide, salt of wormwood, calcium hydroxide or its mixture, wherein [OH -] concentration is 0.2-4.0mol/l, [CO 3 2-] concentration is 0.1-4.0mol/L, [OH -]/([Mg 2+]+[Al 3+]) mol ratio is 0.6-3.5; C. coprecipitation reaction: stir down salts solution and alkaline solution are mixed, then in certain temperature crystallization for some time, generate white precipitate, described mixing speed is for surpassing 80 commentaries on classics/per minutes, crystallization temperature is more than 40 ℃, and crystallization time is more than 0.5 hour, and hybrid mode can be that salts solution adds in the alkaline solution, alkaline solution adds in the salts solution or salts solution and alkaline solution add in the entry simultaneously, the adding mode can be dropping or pour drop rate 5-30 ml/min into; D. separate, washing, drying: will precipitate with centrifugal or suction funnel and separate, be washed with water to neutrality,, promptly get magnesium aluminum-hydrotalcite 70-100 ℃ of drying; E. roasting: place muffle furnace to be warming up to 430-700 ℃ of roasting more than 1 hour the hydrotalcite precursor, promptly get Al-Mg composite metal oxide with the speed of 1-20 ℃/min.
Acidic waste water treatment agent treatment of acidic wastewater process of the present invention is as follows: take by weighing 0.5 gram Al-Mg composite metal oxide, place sulfuric acid, nitric acid and the nitration mixture acid waste water of 30 milliliters of 0.5wt% respectively, stir, the initial pH value of record acid waste water and neutral required time of arrival, centrifugation recycling agent then.Treatment agent of the present invention can be in 2-23 minute time be that the acid waste water of 1.3-1.5 is handled to neutral (pH=7) with the pH value.Through the treatment agent that reclaims is carried out structure determination with the x x ray diffractometer x, the Al-Mg composite metal oxide of finding originally to have the magnesium oxide structure has recovered the stratiform hydrotalcite structure of its precursor behind treatment of acidic wastewater, having formed interlayer anion is the anionic hydrotalcite of solution.The structure memory effect of Here it is hydrotalcite illustrates that treatment agent of the present invention has utilized the structure memory effect of its precursor to reach the purpose of treatment of acidic wastewater.
The regeneration of treatment agent of the present invention and use:, place the speed of muffle furnace 1-20 ℃/min to be warming up to 430-700 ℃ of roasting more than 1 hour, again Al-Mg composite metal oxide with the treatment agent drying that reclaims behind the treatment of acidic wastewater.The regenerated Al-Mg composite metal oxide is used for acid waste water handles, still can make acid waste water reach neutral, and the repeated use of can repeatedly regenerating.
Beneficial effect of the present invention is: the preparation technology of acidic waste water treatment agent is simple, and treatment of acidic wastewater is effective, and treatment agent can be reused repeatedly through roasting regeneration.
Embodiment
The preparation method of acidic waste water treatment agent of the present invention, the effect of treatment of acidic wastewater and regeneration are used, and are further specified by the following examples.
Embodiment 1
The preparation of treatment agent: with 0.36 mole of (88.7 gram) MgSO 47H 2O and 0.1125 mole of (74.9 gram) Al 2(SO 4) 318H 2O is dissolved in 315 ml tap waters and is made into mixing salt solution, with 0.936 mole of (37.4 gram) NaOH and 0.45 mole of (47.7 gram) Na 2CO 3Be dissolved in 315 ml tap waters and be made into mixed ammonium/alkali solutions, under fully stirring, salts solution and alkaline solution are added dropwise in 50 ml tap waters simultaneously, and drop rate 15 ml/min dropwise, be warming up to 80 ℃ of crystallization 4 hours, generate white precipitate, use centrifugation, separated products is washed with tap water, 90 ℃ of dryings, the magnalium ratio is 1.6: 1 a hydrotalcite.Place muffle furnace to be warming up to 500 ℃ of roastings 3 hours the hydrotalcite precursor, promptly get the magnalium ratio and be 1.6: 1 complex metal oxides: Mg with the speed of 1 ℃/min 0.62Al 0.38O (OH) 0.38
Acid waste water treating processes: take by weighing 0.5 gram Al-Mg composite metal oxide Mg 0.62Al 0.38O (OH) 0.38, place sulfuric acid, nitric acid and the nitration mixture acid waste water of 30 milliliters of 0.5wt% respectively, stir the initial pH value of record acid waste water and arrive the neutral required time, centrifugation recycling agent then.Concrete outcome such as table 1.This treatment agent can be in 16-23 minute time be that the acid waste water of 1.3-1.5 is handled to neutral (pH=7) with the pH value.Find that through the treatment agent that reclaims being carried out structure determination Al-Mg composite metal oxide has recovered the stratiform hydrotalcite structure in the acid waste water treating processes.
Table 1
Figure C20061014075300051
Embodiment 2
The preparation of treatment agent: with 0.36 mole of (92.3 gram) Mg (NO 3) 26H 2O and 0.225 mole of (84.4 gram) Al (NO 3) 39H 2O is dissolved in 1000 ml tap waters and is made into mixing salt solution, with 0.936 mole of (52.4 gram) KOH and 0.45 mole of (62.1 gram) K 2CO 3Be dissolved in 235 ml tap waters and be made into mixed ammonium/alkali solutions, under fully stirring, alkaline solution is added dropwise in the salts solution, and drop rate 30 ml/min dropwise, be warming up to 60 ℃ of (crystallization 6 hours, generate white precipitate, use the funnel suction filtration, separated products is washed with tap water, 80 ℃ of dryings, the magnalium ratio is 1.6: 1 a hydrotalcite.Place muffle furnace to be warming up to 430 ℃ of roastings 3 hours the hydrotalcite precursor with the speed of 3 ℃/min, the magnalium ratio is 1.6: 1 a complex metal oxides: Mg 0.62Al 0.38O (OH) 0.38
The acid waste water treating processes is with embodiment 1.Concrete outcome such as table 2.This treatment agent can be in 8-12 minute time be that the acid waste water of 1.3-1.5 is handled to neutral (pH=7) with the pH value.
Table 2
Figure C20061014075300052
Embodiment 3
The preparation of treatment agent: with 0.36 mole of (88.7 gram) MgSO 47H 2O and 0.072 mole of (48.0 gram) Al 2(SO 4) 318H 2O is dissolved in 180 ml tap waters and is made into mixing salt solution, with 1.764 moles of (70.6 gram) NaOH and 0.288 mole of (30.5 gram) Na 2CO 3Be dissolved in 1000 ml tap waters and be made into mixed ammonium/alkali solutions, under fully stirring, salts solution is added dropwise in the alkaline solution, and drop rate 5 ml/min dropwise, be warming up to 100 ℃ of crystallization 0.5 hour, generate white precipitate, use the funnel suction filtration, separated products is washed with tap water, 70 ℃ of dryings, the magnalium ratio is 2.5: 1 a hydrotalcite.Place muffle furnace to be warming up to 550 ℃ of roastings 3 hours the hydrotalcite precursor, promptly get the magnalium ratio and be 2.5: 1 complex metal oxides: Mg with the speed of 5 ℃/min 0.71Al 0.29O (OH) 0.29
Acid waste water treating processes: take by weighing 0.5 gram Al-Mg composite metal oxide Mg 0.71Al 0.29O (OH) 0.29, place sulfuric acid, nitric acid and the nitration mixture acid waste water of 30 milliliters of 0.5wt% respectively, stir the initial pH value of record acid waste water and arrive the neutral required time, centrifugation recycling agent then.Concrete outcome such as table 3.This treatment agent can be in 3-5 minute time be that the acid waste water of 1.3-1.5 is handled to neutral (pH=7) with the pH value.
Table 3
Figure C20061014075300061
Embodiment 4
The preparation of treatment agent: with 0.36 mole of (34.2 gram) MgCl 2With 0.09 mole of (12.0 gram) AlCl 3Be dissolved in 315 ml tap waters and be made into mixing salt solution, with 0.18 mole of (17.3 gram) (NH 4) 2CO 3Be dissolved in the ammoniacal liquor of 100 ml tap waters and 215 milliliter 25% and be made into mixed ammonium/alkali solutions, under fully stirring, salts solution is poured in the alkaline solution, heat up then in 40 ℃ of crystallization 10 hours, generate white precipitate, use the funnel suction filtration, separated products is washed with tap water, 100 ℃ of dryings, the magnalium ratio is 4: 1 a hydrotalcite.Place muffle furnace to be warming up to 600 ℃ of roastings 2 hours the hydrotalcite precursor, promptly get the magnalium ratio and be 4: 1 complex metal oxides: Mg with the speed of 20 ℃/min 0.8Al 0.2O (OH) 0.2
Acid waste water treating processes: take by weighing 0.5 gram Al-Mg composite metal oxide Mg 0.8Al 0.2O (OH) 0.2, place sulfuric acid, nitric acid and the nitration mixture acid waste water of 30 milliliters of 0.5wt% respectively, stir the initial pH value of record acid waste water and arrive the neutral required time, centrifugation recycling agent then.Concrete outcome such as table 4.This treatment agent can be in 3-4 minute time be that the acid waste water of 1.3-1.5 is handled to neutral (pH=7) with the pH value.
Table 4
Figure C20061014075300062
Embodiment 5
The preparation of treatment agent: with 0.36 mole of (88.7 gram) MgSO 47H 2O and 0.018 mole of (12.0 gram) Al 2(SO 4) 318H 2O is dissolved in 315 ml tap waters and is made into mixing salt solution, with 0.238 mole of (2.52 gram) NaOH and 1 mole of (106 gram) Na 2CO 3Be dissolved in 1000 ml tap waters and be made into mixed ammonium/alkali solutions, under fully stirring, alkaline solution is poured in the salts solution, heat up then in 90 ℃ of crystallization 4 hours, generate white precipitate, use the funnel suction filtration, separated products is washed with tap water, 90 ℃ of dryings, the magnalium ratio is 10: 1 a hydrotalcite.Place muffle furnace to be warming up to 700 ℃ of roastings 1 hour the hydrotalcite precursor, promptly get the magnalium ratio and be 10: 1 complex metal oxides: Mg with the speed of 15 ℃/min 0.91Al 0.09O (OH) 0.09
Acid waste water treating processes: take by weighing 0.5 gram Al-Mg composite metal oxide Mg 0.91Al 0.09O (OH) 0.09, place sulfuric acid, nitric acid and the nitration mixture acid waste water of 30 milliliters of 0.5wt% respectively, stir the initial pH value of record acid waste water and arrive the neutral required time, centrifugation recycling agent then.Concrete outcome such as table 5.This treatment agent can be in 2 minutes time be that the acid waste water of 1.3-1.5 is handled to neutral (pH=7) with the pH value.
Table 5
Embodiment 6
The regeneration of treatment agent:, place muffle furnace to be warming up to 500 ℃ of roastings 3 hours, Al-Mg composite metal oxide Mg again with the speed of 5 ℃/min with the treatment agent drying that reclaims behind the treatment of acidic wastewater among the embodiment 3 0.71Al 0.29O (OH) 0.29
The regenerated Al-Mg composite metal oxide is used for acid waste water handles, with embodiment 3, result such as table 6.This manipulation of regeneration agent can be in 3-5 minute time be that the acid waste water of 1.3-1.5 is handled to neutral (pH=7) with the pH value.
Table 6
After repeating the regeneration of above-mentioned treatment agent and wastewater treatment process 6 times, result such as table 7.This manipulation of regeneration agent can be in 4-7 minute time be that the acid waste water of 1.3-1.5 is handled to neutral (pH=7) with the pH value.
Table 7
Figure C20061014075300073
The above only is preferred embodiment of the present invention, and is in order to restriction the present invention, within the spirit and principles in the present invention not all, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (1)

1. renewable industrial acidic wastewater treatment agent that recycles, it is characterized in that: treatment agent is to be the Al-Mg composite metal oxide that precursor obtains through roasting with the magnesium aluminum-hydrotalcite, and it has the crystal mechanism similar to magnesium oxide, it is formed general formula and is: Mg 1-xAl xO (OH) x
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EA201000330A1 (en) * 2007-09-13 2010-10-29 Райнкальк Гмбх THE METHOD OF INCREASING THE PH VALUE OF ACIDAL WATER BODIES
CN101560012A (en) * 2009-03-17 2009-10-21 杭州诚洁环保有限公司 Acidic chemical wastewater pretreating agent and preparation method thereof
CN102229687B (en) * 2011-05-17 2013-02-13 杭州纳琪达纳米科技有限公司 Method for preparing surface lyophobic oleophobic protection treatment agent
CN102351225A (en) * 2011-07-06 2012-02-15 北京科技大学 Method for preparing chloride ion treating medicament
CN108585343A (en) * 2017-08-01 2018-09-28 王建玲 The recycle device and processing method of papermaking enriched water
CN109529795A (en) * 2018-11-30 2019-03-29 昆明理工大学 A kind of hydrogen sulfide adsorbent and preparation method thereof

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JPH11267662A (en) * 1998-03-20 1999-10-05 Mitsubishi Heavy Ind Ltd Method of removing fluorine in waste water of flue gas desulfurization
US20040164028A1 (en) * 2001-06-15 2004-08-26 Avelino Corma Canos Bimetallic catalyst for the treatment of water containing nitrates

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11267662A (en) * 1998-03-20 1999-10-05 Mitsubishi Heavy Ind Ltd Method of removing fluorine in waste water of flue gas desulfurization
US20040164028A1 (en) * 2001-06-15 2004-08-26 Avelino Corma Canos Bimetallic catalyst for the treatment of water containing nitrates

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