CN105152303A - Hydroxylamine modified polyacrylonitrile-iron complex hydrogen peroxide oxidation arsenic removal method - Google Patents
Hydroxylamine modified polyacrylonitrile-iron complex hydrogen peroxide oxidation arsenic removal method Download PDFInfo
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- CN105152303A CN105152303A CN201510678497.7A CN201510678497A CN105152303A CN 105152303 A CN105152303 A CN 105152303A CN 201510678497 A CN201510678497 A CN 201510678497A CN 105152303 A CN105152303 A CN 105152303A
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- azanol
- polyacrylonitrile
- modified polyacrylonitrile
- iron complex
- arsenic
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Abstract
The invention discloses a hydroxylamine modified polyacrylonitrile-iron complex hydrogen peroxide oxidation arsenic removal method. According to the method, by virtue of the oxidation of hydroxylamine modified polyacrylonitrile-iron complex hydrogen peroxide, the trivalent arsenic which is high in toxicity and difficult to process is oxidized to pentavalent arsenic which is easy to process, and the excellent adsorption performance of a hydroxylamine modified polyacrylonitrile-iron complex for the arsenic is used for completely removing the pentavalent arsenic. The method is simple in process, convenient to operate, low in cost, free from producing sludge and capable of effectively removing trivalent arsenic in the water.
Description
Technical field
The present invention relates to the method for a kind of azanol modified polyacrylonitrile-iron complex hydrogen peroxide oxidation arsenic removal.
Background technology
In natural water or lowly water, the Excess free enthalpy of arsenic can produce huge harm to human body, brings out the diseases such as skin carcinoma, lung cancer, bladder cancer and kidney, meanwhile, also can cause the symptoms such as change o f skin colour, hyperkeratosis and neurological disorder.For this reason, national Specification, the arsenic content of tap water must not more than 10 micrograms per litre.An achievement in research being published in " science " shows, in state-owned nearly 2,000 ten thousand people live in arsenic pollute high risk zone, the Arsenic in Drinking Water content of 1500 ten thousand people exceedes often liter of 10 micrograms, exceed 6,000,000 people that have an appointment of often liter of 50 micrograms, the regional total area that arsenic concentration exceedes often liter of 10 micrograms is 580,000 square kilometres.Therefore, in water arsenic exceed standard pollute become problem demanding prompt solution.Arsenic is adsorbed on the effective means that adsorbent surface is considered to remove arsenic from water by employing adsorption method.Gac, virgin iron breeze, ferric oxide coated inorganic material, amino modified silica gel, iron supported ionic exchange resin etc. through metal ion dipping all can be used for the removing of arsenic in water.In natural water or lowly water, the main existing forms of inorganic arsenic is pentavalent arsenic and trivalent arsenic, and arsenious toxicity is 25-60 times of pentavalent arsenic.At present, arsenic-removing adsorption agent is commonly used to arsenious removing efficiency all lower than pentavalent arsenic.Therefore, in order to improve the arsenic removal efficiency of arsenic-removing adsorption agent, normally first trivalent arsenic is oxidized to pentavalent arsenic, then is removed through absorption, cohesion, ion-exchange or membrane process.Publication number is treatment process and the device that the Chinese invention patent of CN1506329A discloses high arsenic underground drinking water, and the method adopts toxicity is large, the unmanageable trivalent arsenic of ozone to be oxidized to pentavalent arsenic, and pentavalent arsenic removes by recycling high-efficient arsenic-removing sorbent completely.What this dearsenicating method adopted is the two step arsenic removal methods of adsorbing after initial oxidation, and process is loaded down with trivial details.Publication number is the method that the Chinese invention patent of CN102910767A discloses the arsenic removal of a kind of activated carbon fiber hydrothermal method carried titanium dioxide photoelectrocatalysioxidization oxidization, adopt photoelectrocatalysis that trivalent arsenic is oxidized to pentavalent arsenic, then utilize the sorbent materials such as titanium dioxide, ferriferous oxide or activated alumina to be removed completely by pentavalent arsenic.The method, except having the loaded down with trivial details shortcoming of process, needs the equipment such as ultraviolet source and optoelectronic pole, improves running cost in photoelectrocatalysioxidization oxidization process.
Summary of the invention
The object of the invention is to prepare azanol modified polyacrylonitrile-iron complex, take hydrogen peroxide as oxygenant, and is applied to arsenious removal in the aqueous solution, the double effects reaching oxidation and remove.
Object of the present invention can be reached by following measure:
(1) vinyl cyanide, Potassium Persulphate, sorbester p17,2% polyvinyl alcohol water solution and deionized water are joined in three mouthfuls of round-bottomed flasks of 250ml, stir under nitrogen protection after 20 minutes, reacting by heating certain hour, filter out solid, after alcohol extraction, vacuum-drying, obtain intermediate polyacrylonitrile;
(2) by polyacrylonitrile and oxammonium hydrochloride, methanol mixed, about the pH to 8 with sodium hydroxide solution regulator solution, stirring reaction under certain temperature, filters out solid, obtains intermediate azanol modified polyacrylonitrile after washing with alcohol, vacuum-drying;
(3) azanol modified polyacrylonitrile is mixed with liquor ferri trichloridi, stirring reaction, filter out solid, after deionized water wash, vacuum-drying, obtain azanol modified polyacrylonitrile-iron complex;
(4) by azanol modified polyacrylonitrile-iron complex and containing trivalent arsenic aqueous solution, hydrogen peroxide is added in mixed solution, mixed solution is vibrated after certain hour, filter out azanol modified polyacrylonitrile-iron complex, make to reach national security drinking water standard containing the high arsenic concentration aqueous solution.
The present invention compared with the prior art tool has the following advantages:
Azanol modified polyacrylonitrile-iron complex synthesis technique involved in the present invention is simple, and adopt hydrogen peroxide as Green Oxidant, oxidizing condition is gentle, high to arsenious oxidation efficiency; Azanol modified polyacrylonitrile-iron complex has excellent adsorption function simultaneously, can by the pentavalent arsenic active adsorption after oxidation, the double effects reaching oxidation and remove; In addition, azanol modified polyacrylonitrile-iron complex can reuse, and does not produce mud, can be used for arsenious arsenic in water and removes.
Object of the present invention also realizes by following concrete measure:
Embodiment 1:
22 milliliters of vinyl cyanide, 0.04 gram of Potassium Persulphate, 0.22 gram of sorbester p17,2.0 milliliter of 2% polyvinyl alcohol water solution and 18 ml deionized water are added respectively in round-bottomed flask; stir under nitrogen protection after 20 minutes; reacting by heating 5 hours; filter out solid, after alcohol extraction, vacuum-drying, obtain intermediate polyacrylonitrile.
After 5 grams of polyacrylonitrile mix with 7.5 grams of oxammonium hydrochlorides, 150 ml methanol, about the pH to 8 with sodium hydroxide solution regulator solution, 60 DEG C of stirring reactions 12 hours, filter out solid, through washing with alcohol, at 50 DEG C vacuum-drying obtain azanol modified polyacrylonitrile after 48 hours.
Be that 0.0025 mol/L ferric chloride aqueous solutions mixes by 5 grams of azanol modified polyacrylonitriles and 500 ml concns, vibrator vibration 24 hours is placed under room temperature, filter out solid, after deionized water wash, at 50 DEG C, vacuum-drying obtains azanol modified polyacrylonitrile-iron complex for 48 hours.
The trivalent arsenic solution being 500 micrograms per litre by 50 milligrams of azanol modified polyacrylonitrile-iron complexes and 20 ml concns mixes, add hydrogen peroxide, the concentration of hydrogen peroxide in mixed solution is made to be 150 mg/litre, stir after 2 ~ 5 hours, leached by azanol modified polyacrylonitrile-iron complex, the arsenic concentration in gained filtrate reaches national security drinking water standard.
Embodiment 2:
24 milliliters of vinyl cyanide, 0.07 gram of Potassium Persulphate, 0.26 gram of sorbester p17,4.0 milliliter of 2% polyvinyl alcohol water solution and 20 ml deionized water are added respectively in round-bottomed flask; stir under nitrogen protection after 20 minutes; reacting by heating 5 hours; filter out solid, after alcohol extraction, vacuum-drying, obtain intermediate polyacrylonitrile.
After 5 grams of polyacrylonitrile mix with 7.5 grams of oxammonium hydrochlorides, 150 ml methanol, about the pH to 8 with sodium hydroxide solution regulator solution, 60 DEG C of stirring reactions 12 hours, filter out solid, through washing with alcohol, at 50 DEG C vacuum-drying obtain azanol modified polyacrylonitrile after 48 hours.
Be that 0.005 mol/L ferric chloride aqueous solutions mixes by 5 grams of azanol modified polyacrylonitriles and 500 ml concns, vibrator vibration 24 hours is placed under room temperature, filter out solid, after deionized water wash, at 50 DEG C, vacuum-drying obtains azanol modified polyacrylonitrile-iron complex for 48 hours.
The trivalent arsenic solution being 1000 micrograms per litre by 50 milligrams of azanol modified polyacrylonitrile-iron complexes and 20 ml concns mixes, add hydrogen peroxide, the concentration of hydrogen peroxide in mixed solution is made to be 200 mg/litre, stir after 2 ~ 5 hours, leached by azanol modified polyacrylonitrile-iron complex, the arsenic concentration in gained filtrate reaches national security drinking water standard.
Claims (3)
1. the method for azanol modified polyacrylonitrile-iron complex hydrogen peroxide oxidation arsenic removal, is characterized in that the method is made up of following four steps:
(1) vinyl cyanide, Potassium Persulphate, sorbester p17,2% polyvinyl alcohol water solution and deionized water are joined in three mouthfuls of round-bottomed flasks of 250ml, stir under nitrogen protection after 20 minutes, reacting by heating certain hour, filter out solid, after alcohol extraction, vacuum-drying, obtain intermediate polyacrylonitrile;
(2) by polyacrylonitrile and oxammonium hydrochloride, methanol mixed, about the pH to 8 with sodium hydroxide solution regulator solution, stirring reaction under certain temperature, filters out solid, obtains intermediate azanol modified polyacrylonitrile after washing with alcohol, vacuum-drying;
(3) azanol modified polyacrylonitrile is mixed with liquor ferri trichloridi, stirring reaction, filter out solid, after deionized water wash, vacuum-drying, obtain azanol modified polyacrylonitrile-iron complex;
(4) by azanol modified polyacrylonitrile-iron complex and containing trivalent arsenic aqueous solution, hydrogen peroxide is added in mixed solution, mixed solution is vibrated after certain hour, filter out azanol modified polyacrylonitrile-iron complex, make to reach national security drinking water standard containing the high arsenic concentration aqueous solution.
2. step described in (1) is prepared in polyacrylonitrile reaction, and the consumption of vinyl cyanide is 19 ~ 24 milliliters; The consumption of Potassium Persulphate is 0.04 ~ 0.07 gram; The consumption of sorbester p17 is 0.20 ~ 0.26 gram; 2% polyvinyl alcohol water solution consumption is 2 ~ 4 milliliters; The consumption of water is 18 ~ 22 milliliters; Temperature of reaction is 60 ~ 72 DEG C; Reaction times is 6 ~ 9h; In the preparation feedback of described azanol modified polyacrylonitrile, the weight ratio of polyacrylonitrile and oxammonium hydrochloride is 1:1.5, and the temperature of reaction of described polyacrylonitrile and oxammonium hydrochloride is 60 ~ 70 DEG C, and the time is 8 ~ 10h; Described step (3) is prepared in the reaction of azanol modified polyacrylonitrile-iron complex, the blending ratio of azanol modified polyacrylonitrile and ferric chloride aqueous solutions is 5 grams: 200 ~ 500 milliliters, the pH of ferric chloride aqueous solutions is 5.5, and concentration is 0.0001 ~ 0.005 mol/L; In described step (4), the trivalent arsenic solution being 500 ~ 2000 micrograms per litre by 50 milligrams of azanol modified polyacrylonitrile-iron complexes and 20 ml concns mixes, add hydrogen peroxide, the concentration of hydrogen peroxide in mixed solution is made to be 100 ~ 200 micrograms per litre, stir after 2 ~ 5 hours, leached by azanol modified polyacrylonitrile-iron complex, the high arsenic concentration aqueous solution in gained filtrate reaches national security drinking water standard.
3. the method for azanol modified polyacrylonitrile according to claim 1-iron complex hydrogen peroxide oxidation arsenic removal, is characterized in that this product is for removal arsenious in the aqueous solution.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540985A (en) * | 2015-12-25 | 2016-05-04 | 河海大学 | Method for degrading organic wastewater by hydroxylamine hydrochloride reinforced iron oxide activated persulfate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04119920A (en) * | 1990-09-06 | 1992-04-21 | Sumitomo Chem Co Ltd | Method for removing arsenic |
| CN1118666A (en) * | 1994-09-16 | 1996-03-20 | 成桂田 | Longevity wheat flour and its making method |
| CN1623921A (en) * | 2003-12-04 | 2005-06-08 | 陈小华 | Process for removing arsenic in water using oxydol as oxidative agent |
| CN101899132A (en) * | 2010-07-26 | 2010-12-01 | 鲁东大学 | Preparation method of polyacrylonitrile adsorbing materials |
| CN104028238A (en) * | 2014-06-16 | 2014-09-10 | 鲁东大学 | Preparation method of arsenic removal adsorbent based on polyacrylonitrile-itaconic acid |
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- 2015-10-20 CN CN201510678497.7A patent/CN105152303A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04119920A (en) * | 1990-09-06 | 1992-04-21 | Sumitomo Chem Co Ltd | Method for removing arsenic |
| CN1118666A (en) * | 1994-09-16 | 1996-03-20 | 成桂田 | Longevity wheat flour and its making method |
| CN1623921A (en) * | 2003-12-04 | 2005-06-08 | 陈小华 | Process for removing arsenic in water using oxydol as oxidative agent |
| CN101899132A (en) * | 2010-07-26 | 2010-12-01 | 鲁东大学 | Preparation method of polyacrylonitrile adsorbing materials |
| CN104028238A (en) * | 2014-06-16 | 2014-09-10 | 鲁东大学 | Preparation method of arsenic removal adsorbent based on polyacrylonitrile-itaconic acid |
Non-Patent Citations (1)
| Title |
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| 李孟等: "《给水处理原理》", 31 December 2013, 武汉理工大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540985A (en) * | 2015-12-25 | 2016-05-04 | 河海大学 | Method for degrading organic wastewater by hydroxylamine hydrochloride reinforced iron oxide activated persulfate |
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Application publication date: 20151216 |