CN103055844A - Catalyst composition for efficiently treating methylene blue dye wastewater and preparation method and application thereof - Google Patents

Catalyst composition for efficiently treating methylene blue dye wastewater and preparation method and application thereof Download PDF

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Publication number
CN103055844A
CN103055844A CN2013100149505A CN201310014950A CN103055844A CN 103055844 A CN103055844 A CN 103055844A CN 2013100149505 A CN2013100149505 A CN 2013100149505A CN 201310014950 A CN201310014950 A CN 201310014950A CN 103055844 A CN103055844 A CN 103055844A
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China
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methylene blue
potassium
blue dye
waste water
carbon monoxide
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CN2013100149505A
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Chinese (zh)
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CN103055844B (en
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周国华
刘晋高
赵贞卓
陈丽雯
高婷婷
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湖北工业大学
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Abstract

The invention discloses a catalyst composition for efficiently treating methylene blue dye wastewater and a preparation method and application thereof. The preparation method comprises the following steps of sequentially adding a potassium compound, a chromium salt, molybdate and citric acid into water, stirring and dissolving, then adding glycol, heating up to 100-130DEG C, continuing stirring to form gel, and heating the gel at 500DEG C-1000DEG C for 5-30 hours so as to obtain the catalyst of ternary composite oxide K2O.Cr2O3.xMoO3 (x=1-8). The catalyst can be used for treating the methylene blue dye wastewater effectively without light or oxidant at normal temperature and pressure; and the degradation rate of methylene blue with concentration of 50mg/L reaches above 90.0% in 60 minutes, and the catalyst can be recycled for multiple times.

Description

Carbon monoxide-olefin polymeric of a kind of efficient processing methylene blue dye waste water and its preparation method and application

Technical field

The invention belongs to the inorganic functional material preparing technical field, relate to a kind of carbon monoxide-olefin polymeric of efficient processing methylene blue dye waste water, relate in particular to a kind of ternary compound oxides K of degradable methylene blue dye waste water 2OCr 2O 3XMoO 3(x=1~8) catalyst and preparation method and application.

Background technology

Organic dye waste water has become one of main pollution source of water body at present.This waste water has that the water yield is large, concentration is high, complicated component, colourity is dark and the characteristics such as difficult degradation.Most of dyestuffs also have toxicity, carcinogenicity, teratogenesis and mutagenic effect.Methylene blue is a kind of important organic chemical synthesis dye of positive ion, and commercial Application is very extensive.For example, can be applicable to the painted of the dyeing of fiber crops, silk fabric, paper and bamboo and wood, be applied to the dyeing of biology, bacterium tissue and be applied to make ink and color lake etc.Methylene blue also will cause containing methylene blue dye waste water to the severe contamination of water body in industrial extensive use.The processing method of organic dye waste water mainly contains bioanalysis, Coagulation Method, high-level oxidation technology, photocatalytic method, absorption method and membrane separation process etc. at present.Bioanalysis is subjected to the impact of the factors such as pH value, temperature, salt and kind of dyes, so that the effect that bioanalysis is processed is not ideal enough.The operating cost of Coagulation Method is higher, the pH value narrow range that the body refuse amount is large and dehydration is difficult, applicable.The high-level oxidation technology cost is high, oxidant commonly used also can show oxidability strong, have the shortcoming such as selective oxidation, and easily introduce impurity in the processing procedure and cause secondary pollution.Photocatalytic method needs the light source irradiation system, is subjected in actual applications weather effect large.Absorption method is subject to the impacts such as suspension in the water and grease, and the adsorbent consumption is large and expense is high.Membrane separation process is divided into electroosmose process, hyperfiltration, nano filtering process and ultrafiltration etc., wherein the advantage of electroosmose process, hyperfiltration, nano filtering process is that the dyestuff clearance is high, can reclaim the dyestuff in the waste water, technique is simple, but the cost of used film is higher, operating pressure is larger, causes the energy consumption of embrane method higher, has affected its industrial applications.Traditional ultrafiltration is difficult to remove low-molecular-weight organic pollution because membrane aperture is larger.Therefore, simply a kind of and catalyst that efficiently process methylene blue dye waste water of exploitation has great importance.

Summary of the invention

In view of the deficiencies in the prior art, the object of the invention is to solve the above-mentioned technical problem that exists in the prior art, carbon monoxide-olefin polymeric of a kind of simple effectively degradation of methylene blue waste water and its preparation method and application is provided.

To achieve these goals, obtained following technical scheme after the present invention studies by lot of experiments:

A kind of carbon monoxide-olefin polymeric of efficient processing methylene blue dye waste water comprises composite oxides, and the general formula of described composite oxides is K 2OCr 2O 3XMoO 3, x=1~8 wherein.

A kind of preparation method of carbon monoxide-olefin polymeric of efficient processing methylene blue dye waste water, described carbon monoxide-olefin polymeric comprises composite oxides, described composite oxides are prepared from as follows:

(1) potassium compound, chromic salts, molybdate and citric acid are added to the water successively, stirring and dissolving, the mol ratio of the potassium in the described potassium compound, the chromium in the chromic salts, the molybdenum in the molybdate, citric acid and water is 1:1:1-8:3-30:250-450;

(2) add ethylene glycol, the ethylene glycol addition is 4 times of citric acid molal quantity, behind the stirring 5-15min, is heated to 100 ℃-130 ℃, continues to stir the formation gel;

(3) gel was calcined 5-30 hours under 500 ℃-1000 ℃, obtained having granular ternary compound oxides K 2OCr 2O 3XMoO 3, x=1~8.

The preparation method of the carbon monoxide-olefin polymeric of described efficient processing methylene blue dye waste water, wherein the water of step (1) employing is deionized water or distilled water.

The preparation method of the carbon monoxide-olefin polymeric of described efficient processing methylene blue dye waste water, wherein the mol ratio of the potassium in the potassium compound described in the step (1), the chromium in the chromic salts, the molybdenum in the molybdate, citric acid and water is 1 ︰, 1 ︰, 4 ︰, 13 ︰ 333.

Described ternary compound oxides K 2OCr 2O 3XMoO 3The preparation method of (x=1~8) catalyst, wherein the calcining heat in the step (3) is 600 ℃-800 ℃, calcination time is 10-20 hours.

The preparation method of the carbon monoxide-olefin polymeric of described efficient processing methylene blue dye waste water, wherein said potassium compound is selected from following one or more: potassium hydroxide, potassium chloride, potash, saleratus, potassium sulfate, potassium acid sulfate, potassium nitrate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, potassium formate, potassium acetate, potassium citrate.

The preparation method of the carbon monoxide-olefin polymeric of described efficient processing methylene blue dye waste water, wherein said chromic salts is one or more in chromic nitrate, chromium sulfate and the chromium chloride.

The preparation method of the carbon monoxide-olefin polymeric of described efficient processing methylene blue dye waste water, wherein said molybdate is that ammonium molybdate is or/and potassium molybdate.

A kind of method of utilizing above-mentioned carbon monoxide-olefin polymeric to process methylene blue dye waste water comprises and turbidly processing in methylene blue dye waste water described carbon monoxide-olefin polymeric is outstanding.

The method of described processing methylene blue dye waste water, preferably the ratio in 0.5~4.0g/L waste water adds described composite oxides K 2OCr 2O 3XMoO 3, under agitation processed 60-120 minute.

Ternary compound oxides K of the present invention 2OCr 2O 3XMoO 3The processing method that (x=1~8) catalyst is applied to methylene blue waste water is: with ternary compound oxides K 2OCr 2O 3XMoO 3(x=1~8) are catalyst, and degradation conditions is: methylene blue concentration is in 1mg/L~90mg/L scope, and the catalyst amount of processing every liter of methylene blue waste water is 0.5~4g, and solution system is in normal temperature and pressure.When the methylene blue solution volume is 40mL, when concentration is 50mg/L, under agitation add catalyst 0.04g, catalytic degradation 60-120 minute, the degradation rate of methylene blue reached more than 90%.The residual solution color is colourless.Residual solution replaced with carry out again catalyst recycle behind the new methylene blue solution and use.The result shows, catalyst is in for the second time circulation, the degradation rate of the methylene blue dye in recycling all reaches more than 90.0% for the third time.

The present invention need not oxidant at normal temperatures and pressures, also need not can effectively process methylene blue dye waste water under the irradiation.Have catalytic degradation efficient high, technological process is simple, and non-secondary pollution produces, and the characteristics such as operating cost is low, and very high actual application value is arranged.

Compared with prior art, the method that the present invention relates to process methylene blue dye waste water has following significant advantage and significant progressive:

(1) method for preparing catalyst of the present invention is simple.

(2) catalyst activity of the present invention is high, in the short period of time quick and efficient degradation pollutant.

(3) method of wastewater treatment of the present invention can carry out at normal temperatures and pressures, and technological process is simple and cost is low.

(4) method of wastewater treatment of the present invention need not to use oxidant, does not also need to adopt any light source irradiation degraded system.

(5) catalyst of the present invention is repeatedly reusable.

The specific embodiment

Form is described in further detail foregoing of the present invention again by the following examples, but this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment, all technology that realizes based on foregoing of the present invention all belong to scope of the present invention.

Embodiment 1

With 0.70g potash (5.1 * 10 -3Mol), 4.04g nine water chromic nitrates (1.0 * 10 -2Mol), 3.58g four water ammonium molybdates (2.9 * 10 -3Mol) and 25.47g citric acid (0.13mol) add successively 60mL(3.33 mol) in the distilled water, stirring and dissolving.Stir 10min after adding 32.28g ethylene glycol (0.52mol), be warmed up to 120 ℃ and continue to stir, until form gel.Gel 600 ℃ of lower heating 20 hours, is obtained the granular ternary compound oxides K of 3.99g 2OCr 2O 3XMoO 3(x=4) catalyst.

Get the ternary compound oxides K that 0.04 gram prepares as stated above 2OCr 2O 3XMoO 3(x=4) catalyst degradation aqueous solution of methylene blue.Methylene blue concentration is 10 mg/L, and volume is 40mL.In the normal temperature and pressure catalysis degradation of methylene blue, supernatant was got in interval set time sampling in centrifugal 10 minutes on centrifuge under stirring action.Adopt spectrophotometer, measure absorbance in methylene blue maximum absorption wave strong point (660nm).Be converted into the concentration of aqueous solution of methylene blue by absorbance-concentration working curve.When degradation time is 60 minutes, the methylene blue degradation rate is 95.58%.

Embodiment 2

With 0.70g potash (5.1 * 10 -3Mol), 4.04g nine water chromic nitrates (1.0 * 10 -2Mol), 3.58g four water ammonium molybdates (2.9 * 10 -3Mol) and 25.47g citric acid (0.13mol) add successively 60mL(3.33 mol) in the distilled water, stirring and dissolving.Stir 10min after adding 32.28g ethylene glycol (0.52mol), be warmed up to 120 ℃ and continue to stir, until form gel.Gel 700 ℃ of lower heating 15 hours, is obtained the granular ternary compound oxides K of 3.95g 2OCr 2O 3XMoO 3(x=4) catalyst.

Get the ternary compound oxides K that 0.04 gram prepares as stated above 2OCr 2O 3XMoO 3(x=4) catalyst degradation aqueous solution of methylene blue.Methylene blue concentration is 50 mg/L, and volume is 40mL.In the normal temperature and pressure catalysis degradation of methylene blue, supernatant was got in interval set time sampling in centrifugal 10 minutes on centrifuge under stirring action.Adopt spectrophotometer, measure absorbance in methylene blue maximum absorption wave strong point (660nm).Be converted into the concentration of aqueous solution of methylene blue by absorbance-concentration working curve.When degradation time is 60 minutes, the methylene blue degradation rate is 99.50%.

Embodiment 3

With 0.70g potash (5.1 * 10 -3Mol), 4.04g nine water chromic nitrates (1.0 * 10 -2Mol), 3.58g four water ammonium molybdates (2.9 * 10 -3Mol) and 25.47g citric acid (0.13mol) add successively 60mL(3.33 mol) in the distilled water, stirring and dissolving.Stir 10min after adding 32.28g ethylene glycol (0.52mol), be warmed up to 120 ℃ and continue to stir, until form gel.Gel 800 ℃ of lower heating 10 hours, is obtained the granular ternary compound oxides K of 3.93g 2OCr 2O 3XMoO 3(x=4) catalyst.

Get the K that 0.04 gram prepares as stated above 2OCr 2O 3XMoO 3(x=4) catalyst degradation aqueous solution of methylene blue.Methylene blue concentration is 10 mg/L, and volume is 40mL.In the normal temperature and pressure catalysis degradation of methylene blue, supernatant was got in interval set time sampling in centrifugal 10 minutes on centrifuge under stirring action.Adopt spectrophotometer, measure absorbance in methylene blue maximum absorption wave strong point (660nm).Be converted into the concentration of aqueous solution of methylene blue by absorbance-concentration working curve.When degradation time is 120 minutes, the methylene blue degradation rate is 92.01%.

Claims (10)

1. an efficient carbon monoxide-olefin polymeric of processing methylene blue dye waste water comprises composite oxides, and it is characterized in that: the general formula of described composite oxides is K 2OCr 2O 3XMoO 3, x=1~8 wherein.
2. efficient preparation method who processes the carbon monoxide-olefin polymeric of methylene blue dye waste water, it is characterized in that: described carbon monoxide-olefin polymeric comprises composite oxides, described composite oxides are prepared from as follows:
(1) potassium compound, chromic salts, molybdate and citric acid are added to the water successively, stirring and dissolving, the mol ratio of the potassium in the described potassium compound, the chromium in the chromic salts, the molybdenum in the molybdate, citric acid and water is 1:1:1-8:3-30:250-450;
(2) add ethylene glycol, the ethylene glycol addition is 4 times of citric acid molal quantity, behind the stirring 5-15min, is heated to 100 ℃-130 ℃, continues to stir the formation gel;
(3) gel was calcined 5-30 hours under 500 ℃-1000 ℃, obtained having granular ternary compound oxides K 2OCr 2O 3XMoO 3, x=1~8.
3. the preparation method of the carbon monoxide-olefin polymeric of described efficient processing methylene blue dye waste water according to claim 2, it is characterized in that: the water that step (1) adopts is deionized water or distilled water.
4. the preparation method of the carbon monoxide-olefin polymeric of described efficient processing methylene blue dye waste water according to claim 2, it is characterized in that: the mol ratio of the potassium described in the step (1) in the potassium compound, the chromium in the chromic salts, the molybdenum in the molybdate, citric acid and water is 1 ︰, 1 ︰, 4 ︰, 13 ︰ 333.
5. the preparation method of the carbon monoxide-olefin polymeric of described efficient processing methylene blue dye waste water according to claim 2, it is characterized in that: the calcining heat in the step (3) is 600 ℃-800 ℃, and calcination time is 10-20 hours.
6. the preparation method of the carbon monoxide-olefin polymeric of described efficient processing methylene blue dye waste water according to claim 2 is characterized in that: described potassium compound is selected from following one or more: potassium hydroxide, potassium chloride, potash, saleratus, potassium sulfate, potassium acid sulfate, potassium nitrate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, potassium formate, potassium acetate, potassium citrate.
7. the preparation method of the carbon monoxide-olefin polymeric of described efficient processing methylene blue dye waste water according to claim 2, it is characterized in that: described chromic salts is one or more in chromic nitrate, chromium sulfate and the chromium chloride.
8. the preparation method of the carbon monoxide-olefin polymeric of described efficient processing methylene blue dye waste water according to claim 2, it is characterized in that: described molybdate is that ammonium molybdate is or/and potassium molybdate.
9. method of utilizing the described carbon monoxide-olefin polymeric of claim 1 to process methylene blue dye waste water is characterized in that: comprise and turbidly processing in methylene blue dye waste water described carbon monoxide-olefin polymeric is outstanding.
10. the method for described processing methylene blue dye waste water according to claim 9, it is characterized in that: the ratio in 0.5 ~ 4.0g/L waste water adds described composite oxides K 2OCr 2O 3XMoO 3, under agitation processed 60-120 minutes.
CN201310014950.5A 2013-01-16 2013-01-16 Preparation method for catalyst composition for efficiently treating methylene blue dye wastewater CN103055844B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104353453A (en) * 2014-10-31 2015-02-18 湖北工业大学 Catalyst composition for degrading methylene blue dye in wastewater, preparation method and application thereof
CN104437468A (en) * 2014-11-05 2015-03-25 湖北工业大学 Catalyst composition for treating wastewater containing methylene blue dye as well as preparation method and application of catalyst composition
CN104971734A (en) * 2015-07-20 2015-10-14 湖北工业大学 Catalyst composition capable of treating methylene blue waste water as well as preparation method and application of catalyst composition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1080285A (en) * 1992-05-13 1994-01-05 希巴-盖吉股份公司 New high-temperature dehydrogenation process
WO2000058272A1 (en) * 1999-03-26 2000-10-05 Mitsubishi Rayon Co., Ltd. Process for producing unsaturated nitrile
CN1962460A (en) * 2005-11-10 2007-05-16 中国科学院合肥物质科学研究院 Lanthanum molybdate (La2Mo2O9) moderate temperature conductor material and its preparation method
CN101733115A (en) * 2009-12-07 2010-06-16 中国科学院山西煤炭化学研究所 Sulfur-tolerant methanation catalyst and preparing method and application thereof
CN102500357A (en) * 2011-10-18 2012-06-20 北京林业大学 Catalyst for catalyzing wet oxidation of cationic azo dye wastewater at normal temperature and normal pressure and preparation method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1080285A (en) * 1992-05-13 1994-01-05 希巴-盖吉股份公司 New high-temperature dehydrogenation process
WO2000058272A1 (en) * 1999-03-26 2000-10-05 Mitsubishi Rayon Co., Ltd. Process for producing unsaturated nitrile
CN1962460A (en) * 2005-11-10 2007-05-16 中国科学院合肥物质科学研究院 Lanthanum molybdate (La2Mo2O9) moderate temperature conductor material and its preparation method
CN101733115A (en) * 2009-12-07 2010-06-16 中国科学院山西煤炭化学研究所 Sulfur-tolerant methanation catalyst and preparing method and application thereof
CN102500357A (en) * 2011-10-18 2012-06-20 北京林业大学 Catalyst for catalyzing wet oxidation of cationic azo dye wastewater at normal temperature and normal pressure and preparation method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
K. IVANOV等: "Oxidation of methanol on sodium modified chromium-molybdenum catalysts", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *
邓凡政等: "MoO3对染料光催化降解性能研究", 《稀有金属》 *
高荣兵等: "La2Mo2O9粉体的制备及表征", 《南昌航空大学学报(自然科学版)》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104353453A (en) * 2014-10-31 2015-02-18 湖北工业大学 Catalyst composition for degrading methylene blue dye in wastewater, preparation method and application thereof
CN104437468A (en) * 2014-11-05 2015-03-25 湖北工业大学 Catalyst composition for treating wastewater containing methylene blue dye as well as preparation method and application of catalyst composition
CN104971734A (en) * 2015-07-20 2015-10-14 湖北工业大学 Catalyst composition capable of treating methylene blue waste water as well as preparation method and application of catalyst composition
CN104971734B (en) * 2015-07-20 2017-12-08 湖北工业大学 A kind of carbon monoxide-olefin polymeric for handling methylene blue waste water and its preparation method and application

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