CN102806092A - Preparation method for catalyst for promoting conversion of ammonia nitrogen in pesticide wastewater - Google Patents
Preparation method for catalyst for promoting conversion of ammonia nitrogen in pesticide wastewater Download PDFInfo
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- CN102806092A CN102806092A CN2012102534875A CN201210253487A CN102806092A CN 102806092 A CN102806092 A CN 102806092A CN 2012102534875 A CN2012102534875 A CN 2012102534875A CN 201210253487 A CN201210253487 A CN 201210253487A CN 102806092 A CN102806092 A CN 102806092A
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Abstract
The invention discloses a preparation method for a catalyst for promoting conversion of ammonia nitrogen in pesticide wastewater. The preparation method comprises the following steps of: mixing a heavy metallic salt mixed solution in which indium metaaluminate is taken as a main component and an organic compound with an alkyl group and aryl, and adding a Grignard reagent and dried ethyl ether and reacting; dissolving a ferric chloride mixed solution, adding NaOH and stirring, precipitating and washing, adding methyl isopropyl ketone and NaOH, dissolving and heating to obtain alumina colloid; mixing products obtained in the steps by an isovolumetric wet method, and drying to obtain a catalyst precursor, baking, drying, and grinding to obtain the catalyst; and the application method comprises the following step of: finally placing the obtained catalyst used as filler in an ammonia still and performing an ammonia still process. The invention aims to provide the catalyst obtained by mixing the nano alumina colloid and the heavy metal organic compound by the isovolumetric wet method; and the ammonia nitrogen in the pesticide wastewater can be directly converted into nitrogen by the catalyst without the conditions of high temperature and pressure, secondary pollution is avoided, and cost is saved.
Description
Technical field
The present invention relates to a kind of method for preparing catalyst that promotes that ammonia nitrogen transforms in the agricultural chemicals waste water, belong to sewage treatment area.
Background technology
Pesticide industry is the industrial wastewater discharge rich and influential family, and agricultural chemicals waste water is meant the waste water that insecticide factory discharges in the pesticide producing process.The waste water quality water yield is unstable, mainly is divided into and contains benzene waste water, contains organophosphor waste water, high concentration brine waste, high-concentration ammonia nitrogenous wastewater, high-concentration phenolic wastewater and mercury-containing waste water.Wherein, agricultural chemicals waste water middle and high concentration ammonia nitrogen concentration can reach every liter of tens thousand of milligram; It is wide that agricultural chemicals waste water pollutes, longer duration, remains of pesticide is big to the health influence, and heavy damage ecological environment, so problem anxious to be solved at present when handling agricultural chemicals waste water middle and high concentration ammonia nitrogen.
At present, the catalyst of improvement sewage is along with science and technology is flourishing increasing, but the reaction of existing catalyst all requires under high-temperature and high-pressure conditions, to carry out; Such as Wang Yaming etc. on document report adopt noble metal catalyst; The technology of catalytic oxidation treatment organic wastewater under HTHP, this method is degradable organic pollutant fully, can reclaim heat energy simultaneously again; But, cause the problem that energy resource consumption is high and disposal cost is expensive because of needing the condition of HTHP.In addition, the ammonia still process method of administering the sewage ammonia nitrogen in high density is a lot of too, and this method steams ammonia through steam, and technology is simple, but ammonia nitrogen removal frank is not high, owing to can only convert ammonia nitrogen into ammonia, can cause the secondary pollution risk problem.Can in patent, not be protected to solving that energy resource consumption is high, cost is high and the report as yet in document of secondary pollution problem in the prior art yet.
Summary of the invention
The energy resource consumption that exists in the prior art is high, cost is high and secondary pollution problem in order to solve; The invention reside in provides a kind of catalyst by nano aluminium oxide colloid and heavy metal organic compound equal-volume wet-mixed; Realized that catalyst directly is converted into nitrogen discharge to the ammonia nitrogen in the agricultural chemicals waste water through ammonia still process under not needing high-temperature and high-pressure conditions; Do not have and cause the secondary pollution risk, the joint medicine cost, reach the national secondary discharge standard.
To achieve these goals, the concrete technical scheme taked of the present invention is:
(1) configuration of heavy metallic salt mixed liquor: the nickel nitrate, periodic acid iridium, bicarbonate cerium, meta-aluminic acid indium, sulfuric acid terbium, platinum chloride, potassium hydroxide, cobalt protoxide, stannous oxide, the rhodium sulphide solution that take by weighing different quality according to a certain ratio;
(2) the heavy metal organic compound is synthetic: choosing the organic compound and the above-mentioned heavy metal salt solution mix that have alkyl and aromatic radical, add a certain amount of grignard reagent and dry diethyl ether, is to react 7～9 hours under 60 ℃～70 ℃ conditions in temperature;
(3) preparation of nano aluminium oxide colloid: get the aluminium chloride that quality is equivalent to 0.25～0.30 times of weight of heavy metal organic compound and mix, add water, be heated to 60 ℃～66 ℃ all after the dissolving, use the NaOH volumetric soiutions pH=10.8 of concentration as 5M; Stir, under constant temperature, generate precipitation of alumina, spend deionised water; Remove how golden salt, add total mass ratio again and be 0.03% methyl isopropyl Ketone, simultaneously 3～5 of the NaOH solution of Dropwise 5 M; Under the ultrasonic wave condition, quicken its dissolving; Drip HCl adjustment pH=4.7 then, water-bath heating 40～60min forms needed alumina gel under 66 ℃～70 ℃ conditions;
(4) wet-mixed: press the nano aluminium oxide colloid and mix, stir, make its decentralization even with mixer with heavy metal organic compound equal-volume;
(5) oven dry: 104 ℃ of bake dryings in baking oven get catalyst precursor;
(6) segmentation roasting: be that 0.28MPa, temperature are 330 ℃ of following roastings 4 hours in negative pressure then, 430 ℃ of roastings 3 hours, 500 ℃ of roastings 1.5 hours, 780 ℃ of following roastings 1 hour, rapid cool drying under normal temperature grinds to form 0.12～0.18mm after the moulding.
Said a kind of method for preparing catalyst that promotes that agricultural chemicals waste water middle and high concentration oxygen nitrogen transforms; It is characterized in that: said different heavy metallic salts by mass percentage, nickel nitrate 5～8%, periodic acid iridium 5～10%, bicarbonate cerium 10～15%, meta-aluminic acid indium 20～28%, sulfuric acid terbium 6～10%, platinum chloride 10～16%, potassium hydroxide 10～20%, cobalt protoxide 2～9%, stannous oxide 1～6%, rhodium sulphide 3～15%.
Said a kind of method for preparing catalyst that promotes that agricultural chemicals waste water middle and high concentration ammonia nitrogen transforms; It is characterized in that: said alkyl compound is two kinds in APES, bromohexadecane yl pyridines, sodium alkyl sulfonate, ethoxylated alkyl sulfate, lauryl sodium sulfate, secondary sodium alkyl benzene sulfonate, the OTAC; Or two or more, compound aromatic base is two or more in benzoic acid, phthalic acid, salicylic acid, aminomethylbenzoic acid, the phenmethylol.
Described catalyst applications method is characterized in that: be placed in the catalyst that obtains in the ammonia still as filler, depth of packing is 2～6cm, and every separated 35cm lays one deck, until cat head.
The invention has the beneficial effects as follows:
(1) can directly be reduced into nitrogen discharge to the ammonia nitrogen in the agricultural chemicals waste water, can not cause secondary pollution environment;
(2) having solved catalyst is not needing to be reduced into nitrogen under ultra-high temperature and the pressure condition, the joint medicine cost;
(3) to agricultural chemicals waste water water quality situation, having selected with the meta-aluminic acid indium is master's catalyst, with strong points.
The inventive method ammonia nitrogen removal frank is high, and reaction speed is fast, and non-secondary pollution produces, and cost is low.
Specific embodiments:
(1) nickel nitrate 5～8%, periodic acid iridium 5～10%, bicarbonate cerium 10～15%, meta-aluminic acid indium 20～28%, sulfuric acid terbium 6～10%, platinum chloride 10～16%, potassium hydroxide 10～20%, cobalt protoxide 2～9%, stannous oxide 1～6%, the rhodium sulphide 3～15% that take by weighing different quality percentage at first according to a certain ratio dispose the heavy metallic salt mixed liquors;
(2) choose that to have alkyl compound be in APES, bromohexadecane yl pyridines, sodium alkyl sulfonate, ethoxylated alkyl sulfate, lauryl sodium sulfate, secondary sodium alkyl benzene sulfonate, the OTAC two or more; Compound aromatic base is two or more and the above-mentioned heavy metal salt solution mix in benzoic acid, phthalic acid, salicylic acid, aminomethylbenzoic acid, the phenmethylol; Adding a certain amount of grignard reagent and dry diethyl ether, is to react 7～9 hours under 60 ℃～70 ℃ conditions in temperature;
(3) get the aluminium chloride that quality is equivalent to 0.25～0.30 times of weight of heavy metal organic compound then and mix, add water, be heated to 60 ℃～66 ℃ all after the dissolving, use the NaOH volumetric soiutions pH=10.8 of concentration as 5M; Stir, under constant temperature, generate precipitation of alumina, spend deionised water; Remove how golden salt, add total mass ratio again and be 0.03% methyl isopropyl Ketone, drip 3～5 of the NaOH solution of 2M simultaneously; Under the ultrasonic wave condition, quicken its dissolving; Drip HCl adjustment pH=4.7 then, water-bath heating 40～60min forms needed alumina gel under 66 ℃～70 ℃ conditions;
(4) press the nano aluminium oxide colloid and mix, stir with mixer with heavy metal organic compound equal-volume, make its decentralization evenly after, 104 ℃ of bake dryings in baking oven, catalyst precursor;
(5) segmentation roasting: be that 0.28MPa, temperature are 330 ℃ of following roastings 4 hours in negative pressure then, 430 ℃ of roastings 3 hours, 500 ℃ of roastings 1.5 hours, 780 ℃ of following roastings 1 hour, rapid cool drying under normal temperature grinds to form 0.12～0.18mm after the moulding;
(6) last, be placed in the gained catalyst in the ammonia still as filler, depth of packing is 2～6cm, every separated 35cm lays one deck, carries out ammonia still process until cat head.
Embodiment 1
At first get nickel nitrate 6g/L, periodic acid iridium 8g/L, bicarbonate cerium 10g/L, meta-aluminic acid indium 25g/L, sulfuric acid terbium 9g/L, platinum chloride 13g/L, potassium hydroxide 15g/L, cobalt protoxide 4g/L, stannous oxide 4g/L, rhodium sulphide 5g/L configuration heavy metallic salt mixed liquor; Choose that to have alkyl compound be that APES, bromohexadecane yl pyridines, sodium alkyl sulfonate and compound aromatic base are benzoic acid, aminomethylbenzoic acid and above-mentioned heavy metal salt solution mix; Adding a certain amount of grignard reagent and dry diethyl ether, is to react 7 hours under 70 ℃ of conditions in temperature; Get the aluminium chloride that quality is equivalent to 0.28 times of weight of heavy metal organic compound then and mix, add water, be heated to 61 ℃ all after the dissolving, use the NaOH volumetric soiutions pH=10.8 of concentration as 5M; Stir, under constant temperature, generate precipitation of alumina, spend deionised water; Remove unnecessary salt, add total mass ratio again and be 0.03% methyl isopropyl Ketone, simultaneously 4 of the NaOH solution of Dropwise 5 M; Under the ultrasonic wave condition, quicken its dissolving; Drip HCl adjustment pH=4.7 then, water-bath heating 40min forms needed alumina gel under 70 ℃ of conditions; Mix both equal-volumes, after the dispersed with stirring, 104 ℃ of bake dryings in baking oven get catalyst precursor; Be that 0.28MPa, temperature are 330 ℃ of following roastings 4 hours in negative pressure then, 430 ℃ of roastings 3 hours, 500 ℃ of roastings 1.5 hours, 780 ℃ of following roastings 1 hour, rapid cool drying under normal temperature grinds to form 0.16mm after the moulding; At last, be placed in the gained catalyst in the ammonia still as filler, depth of packing is 3cm, and every separated 35cm lays one deck, carries out ammonia still process until cat head.
Is certain chemical plant ammonia nitrogen concentration that the agricultural chemicals waste water of 5200mg/L is put into ammonia still and carried out ammonia still process, records the NH of air
3Content is 1.2mg/m
3, the ammonia nitrogen concentration in the waste water is reduced to 0.2mg/L, and ammonia nitrogen removal frank is 99.8%, reaches the national secondary discharge standard.
Embodiment 2
At first get nickel nitrate 7g/L, periodic acid iridium 6g/L, bicarbonate cerium 13g/L, meta-aluminic acid indium 27g/L, sulfuric acid terbium 7g/L, platinum chloride 14g/L, potassium hydroxide 15g/L, cobalt protoxide 2g/L, stannous oxide 3/L g, rhodium sulphide 6g/L configuration heavy metallic salt mixed liquor; Choose that to have alkyl compound be that APES, bromohexadecane yl pyridines, sodium alkyl sulfonate and compound aromatic base are benzoic acid, aminomethylbenzoic acid and above-mentioned heavy metal salt solution mix; Adding a certain amount of grignard reagent and dry diethyl ether, is to react 9 hours under 64 ℃ of conditions in temperature; Get the aluminium chloride that quality is equivalent to 0.27 times of weight of heavy metal organic compound then and mix, add water, be heated to 63 ℃ all after the dissolving, use the NaOH volumetric soiutions pH=10.3 of concentration as 5M; Stir, under constant temperature, generate precipitation of alumina, spend deionised water; Remove unnecessary salt, add total mass ratio again and be 0.03% methyl isopropyl Ketone, simultaneously 5 of the NaOH solution of Dropwise 5 M; Under the ultrasonic wave condition, quicken its dissolving; Drip HCl adjustment pH=4.7 then, water-bath heating 45min forms needed alumina gel under 68 ℃ of conditions;
Mix both equal-volumes, after the dispersed with stirring, 106 ℃ of bake dryings in baking oven get catalyst precursor; Be that 0.28MPa, temperature are 360 ℃ of following roastings 3 hours in negative pressure then, 460 ℃ of roastings 2 hours, 660 ℃ of roastings 1.5 hours, 860 ℃ of following roastings 2.5 hours, rapid cool drying under normal temperature grinds to form 0.17mm after the moulding; At last, be placed in the gained catalyst in the ammonia still as filler, depth of packing is 5cm, and every separated 36cm lays one deck, carries out ammonia still process until cat head.
Is certain pharmacy ammonia nitrogen concentration that the agricultural chemicals waste water of 6542mg/L is put into ammonia still and carried out ammonia still process, records the NH of air
3Content is 1.5mg/m
3, the ammonia nitrogen concentration in the waste water is reduced to 0.15mg/L, and ammonia nitrogen removal frank is 99.8%, reaches the national secondary discharge standard.
Embodiment 3
At first get nickel nitrate 8g/L, periodic acid iridium 5g/L, bicarbonate cerium 11g/L, meta-aluminic acid indium 23g/L, sulfuric acid terbium 6g/L, platinum chloride 12g/L, potassium hydroxide 18g/L, cobalt protoxide 5g/L, stannous oxide 6g/L, rhodium sulphide 6g/L configuration heavy metallic salt mixed liquor; Choose that to have alkyl compound be that APES, bromohexadecane yl pyridines, sodium alkyl sulfonate and compound aromatic base are benzoic acid, aminomethylbenzoic acid and above-mentioned heavy metal salt solution mix; Adding a certain amount of grignard reagent and dry diethyl ether, is to react 4 hours under 72 ℃ of conditions in temperature; Get the aluminium chloride that quality is equivalent to 0.30 times of weight of heavy metal organic compound then and mix, add water, be heated to 72 ℃ all after the dissolving, use the NaOH volumetric soiutions pH=10.4 of concentration as 3M; Stir, under constant temperature, generate precipitation of alumina, spend deionised water; Remove unnecessary salt, add total mass ratio again and be 0.03% methyl isopropyl Ketone, drip 5 of the NaOH solution of 2M simultaneously; Under the ultrasonic wave condition, quicken its dissolving; Drip HCl adjustment pH=4.6 then, water-bath heating 45min forms needed alumina gel under 72 ℃ of conditions;
Mix both equal-volumes, after the dispersed with stirring, 102 ℃ of bake dryings in baking oven get catalyst precursor; Be that 0.28MPa, temperature are 330 ℃ of following roastings 4 hours in negative pressure then, 430 ℃ of roastings 3 hours, 500 ℃ of roastings 1.5 hours, 780 ℃ of following roastings 1 hour, rapid cool drying under normal temperature grinds to form 0.18mm after the moulding; At last, be placed in the gained catalyst in the ammonia still as filler, depth of packing is 3cm, and every separated 45cm lays one deck, carries out ammonia still process until cat head.
Is certain chemical plant ammonia nitrogen concentration that the agricultural chemicals waste water of 6800mg/L is put into ammonia still and carried out ammonia still process, records the NH of air
3Content is 1.3mg/m
3, the ammonia nitrogen concentration in the waste water is reduced to 0.2mg/L, and ammonia nitrogen removal frank is 99.8%, reaches the national secondary discharge standard
Claims (3)
1. method for preparing catalyst that promotes that agricultural chemicals waste water middle and high concentration ammonia nitrogen transforms is characterized in that:
(1) configuration of heavy metallic salt mixed liquor: the nickel nitrate, periodic acid iridium, bicarbonate cerium, meta-aluminic acid indium, sulfuric acid terbium, platinum chloride, potassium hydroxide, cobalt protoxide, stannous oxide, the rhodium sulphide solution that take by weighing different quality according to a certain ratio;
(2) the heavy metal organic compound is synthetic: choosing the organic compound and the above-mentioned heavy metal salt solution mix that have alkyl and aromatic radical, add a certain amount of grignard reagent and dry diethyl ether, is to react 7～9 hours under 60 ℃～70 ℃ conditions in temperature;
(3) preparation of nano aluminium oxide colloid: get the aluminium chloride that quality is equivalent to 0.25～0.30 times of weight of heavy metal organic compound and mix, add water, be heated to 60 ℃～66 ℃ all after the dissolving, use the NaOH volumetric soiutions pH=10.8 of concentration as 5M; Stir, under constant temperature, generate precipitation of alumina, spend deionised water; Remove unnecessary salt, add total mass ratio again and be 0.03% methyl isopropyl Ketone, simultaneously 3～5 of the NaOH solution of Dropwise 5 M; Under the ultrasonic wave condition, quicken its dissolving; Drip HCl adjustment pH=4.7 then, water-bath heating 40～60min forms needed alumina gel under 66 ℃～70 ℃ conditions;
(4) wet-mixed: press the nano aluminium oxide colloid and mix, stir, make its decentralization even with mixer with heavy metal organic compound equal-volume;
(5) oven dry: 104 ℃ of bake dryings in baking oven get catalyst precursor;
(6) segmentation roasting: be that 0.28MPa, temperature are 330 ℃ of following roastings 4 hours in negative pressure then, 430 ℃ of roastings 3 hours, 500 ℃ of roastings, 780 ℃ of following roastings in 1.5 hours 1 hour, rapid cool drying under normal temperature grinds to form 0.12～0.18mm after the moulding.
2. according to the said a kind of method for preparing catalyst that promotes that agricultural chemicals waste water middle and high concentration ammonia nitrogen transforms of claim 1; It is characterized in that: said different heavy metallic salts by mass percentage, nickel nitrate 5～8%, periodic acid iridium 5～10%, bicarbonate cerium 10～15%, meta-aluminic acid indium 20～28%, sulfuric acid terbium 6～10%, platinum chloride 10～16%, potassium hydroxide 10～20%, cobalt protoxide 2～9%, stannous oxide 1～6%, rhodium sulphide 3～15%.
3. according to the said a kind of method for preparing catalyst that promotes that agricultural chemicals waste water middle and high concentration ammonia nitrogen transforms of claim 1; It is characterized in that: said alkyl compound is two or more in APES, bromohexadecane yl pyridines, sodium alkyl sulfonate, ethoxylated alkyl sulfate, lauryl sodium sulfate, secondary sodium alkyl benzene sulfonate, the OTAC, and compound aromatic base is two or more in benzoic acid, phthalic acid, salicylic acid, aminomethylbenzoic acid, the phenmethylol.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0975995A (en) * | 1995-09-19 | 1997-03-25 | Hitachi Ltd | Removing system of high concentration ammonia nitrogen |
| JP2004025020A (en) * | 2002-06-25 | 2004-01-29 | Ishikawajima Harima Heavy Ind Co Ltd | Method of treating waste liquor containing ammonia and treatment apparatus |
| US20040062705A1 (en) * | 2002-09-26 | 2004-04-01 | Philippe Leduc | Process for lowering the content of organic matter and nitrogenous products contained in bromide-containing effluents |
| CN1502407A (en) * | 2002-11-19 | 2004-06-09 | 南昌大学 | Catalyst for purifying exhausted gas of car and preparation process thereof |
| US20050215429A1 (en) * | 2004-03-23 | 2005-09-29 | Nissan Motor Co., Ltd | Catalyst powder, exhaust gas purifying catalyst, and method of producing the catalyst powder |
| CN101703935A (en) * | 2009-11-19 | 2010-05-12 | 浙江工业大学 | Load type metal catalyst and preparation method thereof |
| CN102039125A (en) * | 2009-10-13 | 2011-05-04 | 中国科学院生态环境研究中心 | Preparation and application method of supported bimetallic catalyst for removing nitrate in water |
-
2012
- 2012-07-18 CN CN201210253487.5A patent/CN102806092B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0975995A (en) * | 1995-09-19 | 1997-03-25 | Hitachi Ltd | Removing system of high concentration ammonia nitrogen |
| JP2004025020A (en) * | 2002-06-25 | 2004-01-29 | Ishikawajima Harima Heavy Ind Co Ltd | Method of treating waste liquor containing ammonia and treatment apparatus |
| US20040062705A1 (en) * | 2002-09-26 | 2004-04-01 | Philippe Leduc | Process for lowering the content of organic matter and nitrogenous products contained in bromide-containing effluents |
| CN1502407A (en) * | 2002-11-19 | 2004-06-09 | 南昌大学 | Catalyst for purifying exhausted gas of car and preparation process thereof |
| US20050215429A1 (en) * | 2004-03-23 | 2005-09-29 | Nissan Motor Co., Ltd | Catalyst powder, exhaust gas purifying catalyst, and method of producing the catalyst powder |
| CN102039125A (en) * | 2009-10-13 | 2011-05-04 | 中国科学院生态环境研究中心 | Preparation and application method of supported bimetallic catalyst for removing nitrate in water |
| CN101703935A (en) * | 2009-11-19 | 2010-05-12 | 浙江工业大学 | Load type metal catalyst and preparation method thereof |
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