CN103406089B - Method for preparation of rime-like titanate by taking organic matters in methacrylic acid wastewater as template agent - Google Patents

Method for preparation of rime-like titanate by taking organic matters in methacrylic acid wastewater as template agent Download PDF

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CN103406089B
CN103406089B CN201310305418.9A CN201310305418A CN103406089B CN 103406089 B CN103406089 B CN 103406089B CN 201310305418 A CN201310305418 A CN 201310305418A CN 103406089 B CN103406089 B CN 103406089B
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titanate
methacrylic acid
template
waste water
rime
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CN201310305418.9A
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Chinese (zh)
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CN103406089A (en
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王敏
张东
周波生
方得安
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沈阳理工大学
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Abstract

The invention relates to a method for preparation of a rime-like titanate by taking organic matters in methacrylic acid wastewater as a template agent. The method comprises the technical steps of: 1. letting wastewater enter an evaporator directly, recovering sodium acetate, when an evaporation residual waste liquor accounts for 3%-10% of the volume of the original wastewater, conducting discharge to obtain a sticky complexing template agent; 2. according to the ratio of the mole number of alkaline-earth metals to the mass of the complexing template agent of not greater than 1:400, weighing a nitrate, dissolving it in a 60DEG C water bath, adding the product into the sticky complexing template agent obtained in step 1 to obtain a jelly; 3. weighing tetra-n-butyl titanate according to the mole ratio of alkaline-earth metal ions to titanium at 1:1, carrying out stirring at 60DEG C, adding tetra-n-butyl titanate into the jelly prepared in step 2, further performing stirring for 1h, and conducting drying at 105DEG C to obtain a titanate gel; 4. calcining the gel prepared in step 3 for 8h at 600-900DEG C, thus obtaining a rime-like titanate adsorbent. The method provided in the invention has the advantages of simple process, stability, easy control, and low cost.

Description

The organic matter in methacrylic acid waste water of take is template rime shape processed titanate method

Technical field

The present invention relates to water-treatment technology field, particularly utilizing organic matter in methacrylic acid waste water is complexing template rime shape processed titanate adsorbent method.

Background technology

Heavy metal is the polluter that a class toxicity is large, can not be biodegradable, can accumulate in vivo.Processing method for heavy metal wastewater thereby mainly contains chemical precipitation method, absorption method, ion-exchange and electrochemical process etc., in these methods, absorption method because of its have adapt to wide, treatment effect is good, non-secondary pollution, when processing waste water, can reclaim utility, in heavy metal containing wastewater treatment, be paid attention to widely.The core of absorption method is the exploitation of adsorbent, at present, people have developed a lot of adsorbents, as active carbon, bentonite, flyash, zeolite and artificial macromolecule etc., but these adsorbents in actual applications, exist regeneration difficulty or adsorption capacity lower or reuse the problems such as poor stability.By comparison, Nano titanate, comprises nano barium titanate calcium, nano-sized magnesium titanate, nano strontium titanate and nano barium phthalate etc., there is adsorption capacity large, stable chemical nature, easily regeneration, strong to heavy metal detergent power in water, steady performance, a kind of good heavy metal absorbent (east, Hou Ping, chemical journal, 2009,67 12 phases of volume: p1336-1342; Open east, Su Huidong, Gao Hong, spectroscopy and spectrum analysis 2008,28 1 phases of volume: p218-221).But nano-powder, because its particle diameter is trickle, easily runs off in actual applications, recycling difficulty.And the large titanate of particle diameter is low to the adsorption capacity of heavy metal, without actual application value.In order to prepare the titanate sorbing material of the high absorption property of easy recovery, it is template that inventor once adopted respectively the materials such as stalk and D311 resin balls, has prepared a titanate (east of special appearance, Wang Min, Tan Yuling, chemical journal, 2010,16 phases, p1641-1648; Dong Zhang, Chun-li Zhang, Pin Zhou, Journal of Hazardous Materials,, 186 volume 2-3 phases, p971 – 977 in 2011).These materials, because it has special surface topography, the specific area of super large, and in water, in heavy metal adsorption, show excellent performance, and easily recycling.When but these titanates synthesize, all adopt sol-gal process, need the organic acids such as a large amount of acetic acid, citric acid as catalysis and complexing agent, these make the synthetic cost of titanate very high.

In methacrylic acid waste water, contain a large amount of acetic acid, acrylic acid, the materials such as methacrylic acid and aldehydes, in order to reclaim acetic acid wherein, can adopt agitating heating evaporation.In heating evaporation process, can there is polymerization in methacrylic acid, acrylic acid isoreactivity monomer, after evaporation finishes, in substrate, can generate the methacrylic acid that is rich in the groups such as carboxyl and the mixed polymers of aldehydes of certain degree of polymerization, evaporate simultaneously and in substrate, also can leave the not acetic acid of volatilization of part.The long-chain of mixed polymers has template effect, and polymeric long end of the chain carboxyl can play complexing and peptizaiton, and acetic acid can play catalysis and complexing to sol-gel process.It is complexing dispersion and template that the present invention utilizes the organic matter in methacrylic acid waste water, prepares rime shape titanate heavy metal absorbent, and research and the application of this respect have no report.

Summary of the invention

The technical problem to be solved in the present invention is, provides that a kind of to utilize the organic matter in methacrylic acid waste water be complexing dispersion and template, prepares rime shape titanate heavy metal absorbent

A kind of organic matter that utilizes in methacrylic acid waste water prepare rime shape titanate adsorbent method for complexing template.

The technical scheme adopting is:

Complexing template rime shape processed titanate adsorbent method in methacrylic acid waste water, in described metering system acid producing waste water, methacrylic acid and/or acrylic acid and/or aldehydes gross mass percentage composition are not less than 0.1%, and the method comprises following processing step:

Step 1, waste water directly enters evaporimeter, agitating heating is evaporated water and acetic acid, in alkali and after, reclaim sodium acetate.And materials such as methacrylic acid, acrylic acid and aldehydes in water aggregate into macromolecular substances, when evaporation residual waste solution be raw wastewater volume 3%-10% time, discharging, obtains thick, the complexing template rich carboxylic, the mixed polymers of the methacrylic acid of take is main component.

Step 2, is not more than 1:400 by the ratio of alkaline-earth metal molal quantity and complexing template quality, takes the nitrate of alkaline-earth metal, in 60 ℃ of water-baths, continuing under intense agitation, joining in the thick complexing template that step 1 obtains, dispersed with stirring forms uniform jelly.

Step 3, in molar ratio, alkaline-earth metal ions: titanium is that 1:1 measures tetra-n-butyl titanate, at 60 ℃, continues under intense agitation, and tetra-n-butyl titanate is added dropwise in jelly prepared by step 2, drips off rear continuation and stirs 1h.Be mixed even after, under 105 ℃ of conditions, dry, make titanate gelinite.

Step 4, gelinite prepared by step 3 is placed in cabinet-type electric furnace, in 600-900 ℃, calcines 8h in air atmosphere, naturally cools to room temperature in stove, obtains rime shape titanate adsorbent, for water heavy metal adsorption.

In above-mentioned step 1, during evaporation, best residual waste solution volume is 5%-8% of raw wastewater volume.

In above-mentioned step 2, the alkaline earth nitrate adding is a kind of in the nitrate of magnesium, calcium, strontium, barium.

In above-mentioned step 2, the molal quantity of the alkaline earth nitrate adding and complexing template ratio the best in quality are 1:500-1:5000.

Above-mentioned step 4, the calcining of the titanate gel containing the template optimum temperature of preparation is 750-850 ℃.

Of the present inventionly prepare rime shape titanate adsorbent processed and belong to twice laid, when greatly reducing methacrylic acid waste water COD, prepare heavy metal absorbent, strong to heavy metal adsorption accumulation ability, applicable heavy metal scope is wide, and technique is simple, stable, be easy to control, cost is low, has very high economy, society and environmental benefit.

Accompanying drawing explanation

Fig. 1 is the infrared spectrogram of sample.

Fig. 2 is the SEM figure of rime shape nano barium titanate calcium adsorbent.

Fig. 3 is the XRD collection of illustrative plates of rime shape nano barium titanate calcium adsorbent.

The spectral line in Fig. 1 1-with template that in methacrylic acid waste water prepared by organic matter wherein; Spectral line 2-calcium titanate gel; The calcium titanate gel of spectral line 3-contain template; Spectral line 4-rime shape nano barium titanate calcium.

The specific embodiment

Herein, term " methacrylic acid waste water " represents acrylic or methacrylic acid producing waste water, is called for short " waste water ".

Below by example, method of the present invention and technology are illustrated, in practical application, are not limited to this:

Table 1. methacrylic acid waste water component list (quality percentage composition) ? H 2O Toluene Acetic acid Acrylic acid Methacrylic acid Formaldehyde Other organic matter COD（mg/L） Methacrylic acid waste water 90.12% 0.21% 7.23% 0.79% 0.34% 1.03% 0.28% 101667

Embodiment mono-

The waste water that the present embodiment is used is methacrylic acid waste water, and composition is in Table 1; The present embodiment method is as follows:

Get 10L waste water, heating evaporation moisture and acetic acid wherein, recovery of acetic acid sodium.When waste water surplus is about 500mL, discharging, obtains complexing template.Take 0.2mol calcium nitrate, in 60 ℃ of water-baths, under stirring condition, dissolve in 100g complexing template, continue to stir 1h, be uniformly dispersed, obtain jelly.Keep 60 ℃ of water-baths, continue, under vigorous stirring, 0.2moL tetra-n-butyl titanate to be added dropwise in calcic jelly.Continue to stir after lh, jelly is placed in to baking oven, dry at 105 ℃, obtain calcium titanate gel, in 750 ℃, in air atmosphere, calcine 8h, in stove, naturally cool to room temperature, obtain rime shape nano barium titanate calcium adsorbent.

Embodiment bis-

Take 0.02mol calcium nitrate, in 60 ℃ of water-baths, under stirring condition, dissolve in 100g embodiment mono-and obtain in complexing template, continue to stir 1h, be uniformly dispersed, obtain jelly.Keep 60 ℃ of water-baths, continue, under vigorous stirring, 0.02moL tetra-n-butyl titanate to be added dropwise in calcic jelly.Continue to stir after lh, jelly is placed in to baking oven, dry at 105 ℃, obtain calcium titanate gel, in 750 ℃, in air atmosphere, calcine 8h, in stove, naturally cool to room temperature, obtain rime shape nano barium titanate calcium adsorbent.

Embodiment tri-

Take 0.2mol calcium nitrate, in 60 ℃ of water-baths, under stirring condition, dissolve in 100g embodiment mono-and obtain in complexing template, continue to stir 1h, be uniformly dispersed, obtain jelly.Keep 60 ℃ of water-baths, continue, under vigorous stirring, 0.2moL tetra-n-butyl titanate to be added dropwise in calcic jelly.Continue to stir after lh, jelly is placed in to baking oven, dry at 105 ℃, obtain calcium titanate gel, in 850 ℃, in air atmosphere, calcine 8h, in stove, naturally cool to room temperature, obtain rime shape nano barium titanate calcium adsorbent.

Embodiment tetra-

The waste water that the present embodiment is used is methacrylic acid waste water, and composition is in Table 1; The present embodiment method is as follows:

Get 10L waste water, heating evaporation moisture and acetic acid wherein, recovery of acetic acid sodium.When waste water surplus is about 800mL, discharging, obtains complexing template.Take 0.2mol calcium nitrate, in 60 ℃ of water-baths, under stirring condition, dissolve in 100g complexing template, continue to stir 1h, be uniformly dispersed, obtain jelly.Keep 60 ℃ of water-baths, continue, under vigorous stirring, 0.2moL tetra-n-butyl titanate to be added dropwise in calcic jelly.Continue to stir after lh, jelly is placed in to baking oven, dry at 105 ℃, obtain calcium titanate gel, in 750 ℃, in air atmosphere, calcine 8h, in stove, naturally cool to room temperature, obtain rime shape nano barium titanate calcium adsorbent.

Embodiment five

Take 0.02mol calcium nitrate, in 60 ℃ of water-baths, under stirring condition, dissolve in 100g embodiment tetra-and obtain in complexing template, continue to stir 1h, be uniformly dispersed, obtain jelly.Keep 60 ℃ of water-baths, continue, under vigorous stirring, 0.02moL tetra-n-butyl titanate to be added dropwise in calcic jelly.Continue to stir after lh, jelly is placed in to baking oven, dry at 105 ℃, obtain calcium titanate gel, in 750 ℃, in air atmosphere, calcine 8h, in stove, naturally cool to room temperature, obtain rime shape nano barium titanate calcium adsorbent.

Embodiment six

Take 0.2mol strontium nitrate, in 60 ℃ of water-baths, under stirring condition, dissolve in 100g embodiment 1 and obtain in complexing template, continue to stir 1h, be uniformly dispersed, obtain jelly.Keep 60 ℃ of water-baths, continue, under vigorous stirring, 0.02moL tetra-n-butyl titanate to be added dropwise to containing in strontium jelly.Continue to stir after lh, jelly is placed in to baking oven, dry at 105 ℃, obtain strontium titanates gel, in 750 ℃, in air atmosphere, calcine 8h, in stove, naturally cool to room temperature, obtain rime shape nano strontium titanate adsorbent.

Embodiment seven

In order to investigate the absorption property of the rime shape titanate ABSORBENTS ABSORPTION metal obtaining in embodiment mono-to six, get a certain amount of heavy metal lead ion in 50mL scale tool plug conical flask, adjust pH 4, water constant volume is to 20mL, more accurately adds 0.02 g titanate adsorbent, cover tightly lid, on oscillator, vibration absorption 10min, takes out, and filters, with flame atomic absorption spectrophotometer, survey concentration plumbous in supernatant, calculate adsorbance.The results are shown in Table 2:

The adsorbent of preparing in table 2 embodiment 1-6 is to plumbous absorption property ? Initial concentration (mg/L) Equilibrium concentration (mg/L) Unit adsorbance (mg/g) Embodiment 1-calcium titanate 500 0 500 Embodiment 2-calcium titanate 500 0 500 Embodiment 3-calcium titanate 500 0 500 Embodiment 4-calcium titanate 500 0 500 Embodiment 5-calcium titanate 500 0 500 Embodiment 6-strontium titanates 500 19.54 480.46

Embodiment eight

The recovery of regeneration and heavy metal after the rime shape titanate adsorbent that obtains in embodiment mono-to six is used: the titanate of heavy metal of having got absorption in embodiment seven, wash 3 times, the salpeter solution that adds respectively 5mL 1mol/L, vibration wash-out 5 minutes, with the content of the lead ion in atomic absorption detecting supernatant, calculate the wash-out rate of recovery.The results are shown in Table 3:

Table 3: the wash-out rate of recovery ? Eluent lead concentration (mg/L) Wash-out yield (mg) The rate of recovery (%) Embodiment 1-calcium titanate 1988 9.94 99.40 Embodiment 2-calcium titanate 1967 9.835 98.35 Embodiment 3-calcium titanate 1959 9.795 97.95 Embodiment 4-calcium titanate 1998 9.99 99.90 Embodiment 5-calcium titanate 2035 10.18 101.75 Embodiment 6-strontium titanates 1916 9.58 99.70

Claims (5)

1. the organic matter in methacrylic acid waste water of take is template rime shape processed titanate adsorbent method, in described methacrylic acid waste water, methacrylic acid and/or acrylic acid and/or aldehydes gross mass percentage composition are not less than 0.1%, it is characterized in that the method comprises following processing step:
Step 1, waste water directly enters evaporimeter, agitating heating is evaporated water and acetic acid, in alkali and after, reclaim sodium acetate; And methacrylic acid, acrylic acid and aldehyde material in water aggregates into macromolecular substances, when evaporation residual waste solution be raw wastewater volume 3%-10% time, discharging, obtains thick, the complexing template rich carboxylic, the mixed polymers of the methacrylic acid of take is main component;
Step 2, is not more than 1:400 by the ratio of alkaline-earth metal molal quantity and complexing template quality, takes the nitrate of alkaline-earth metal, in 60 ℃ of water-baths, continuing under intense agitation, joining in the thick complexing template that step 1 obtains, dispersed with stirring forms uniform jelly;
Step 3, in molar ratio, alkaline-earth metal ions: titanium is that 1:1 measures tetra-n-butyl titanate, at 60 ℃, continues under intense agitation, and tetra-n-butyl titanate is added dropwise in jelly prepared by step 2, drips off rear continuation and stirs 1h; Be mixed even after, under 105 ℃ of conditions, dry, make titanate gelinite;
Step 4, gelinite prepared by step 3 is placed in cabinet-type electric furnace, in 600-900 ℃, calcines 8h in air atmosphere, naturally cools to room temperature in stove, obtains rime shape titanate adsorbent, for water heavy metal adsorption.
2. according to claim 1 to take organic matter in methacrylic acid waste water be template rime shape processed titanate adsorbent method, it is characterized in that in described step 1, and during evaporation, best residual waste solution volume is 5%-8% of raw wastewater volume.
3. according to claim 1 to take organic matter in methacrylic acid waste water be template rime shape processed titanate adsorbent method, it is characterized in that in described step 2, and the alkaline earth nitrate adding is a kind of in the nitrate of magnesium, calcium, strontium, barium.
It is 4. according to claim 1 that to take organic matter in methacrylic acid waste water be template rime shape processed titanate adsorbent method, it is characterized in that in described step 2, the molal quantity of the alkaline earth nitrate adding and complexing template ratio the best in quality are 1:500-1:5000.
5. according to claim 1 to take organic matter in methacrylic acid waste water be template rime shape processed titanate adsorbent method, it is characterized in that described step 4, and the calcining of the titanate gel containing the template optimum temperature of preparation is 750-850 ℃.
CN201310305418.9A 2013-07-22 2013-07-22 Method for preparation of rime-like titanate by taking organic matters in methacrylic acid wastewater as template agent CN103406089B (en)

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