CN103771366B - The method of a kind of yellow phosphorus oxidation arsenic removal - Google Patents
The method of a kind of yellow phosphorus oxidation arsenic removal Download PDFInfo
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- CN103771366B CN103771366B CN201310747146.8A CN201310747146A CN103771366B CN 103771366 B CN103771366 B CN 103771366B CN 201310747146 A CN201310747146 A CN 201310747146A CN 103771366 B CN103771366 B CN 103771366B
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- yellow phosphorus
- oxidation
- oxide catalyst
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- oxygenant
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Abstract
The present invention discloses the method for a kind of yellow phosphorus oxidation arsenic removal, under normal pressure, mix the yellow phosphorus under dearsenic agent solution and molten state to interact, arsenic in yellow phosphorus is oxidized to solubility arsenide enter aqueous phase and take off and remove, wherein mix dearsenic agent solution and comprise basis oxygenant, oxide catalyst and enhancing oxygenant, after repeatedly washing finally by ultrapure water, namely obtain dearsenification yellow phosphorus. In the present invention, under mixing dearsenic agent effect, yellow phosphorus forms good emulsifying particulate state, considerably increase the contact area of dearsenic agent and yellow phosphorus, adopt segmentation repeatedly to add the mode of oxidation toughener, ensure persistence and the high efficiency of whole dearsenification process dearsenification effect, oxide catalyst makes dearsenification reaction more rapidly and efficiently carry out, realize the high receipts rate of yellow phosphorus while ensure that efficient dearsenification, it is a kind of efficient, safe, economic arsenic removing method, there is good economic benefit and social benefit.
Description
Technical field
The present invention relates to yellow phosphorus manufacture field in sulphur dioxide of phosphor chemical industry, it relates to the method for a kind of yellow phosphorus oxidation arsenic removal.
Background technology
Yellow phosphorus is a kind of important phosphorous chemical industry basic material. Industrial yellow phosphorus contains multiple trace impurity, seriously have impact on the development of its application and fine phosphorus chemical, and wherein arsenic is a kind of main impurity, owing to arsenic is a kind of severe toxicity element, at application occasions such as food, medicine and makeup, the requirement of arsenic content is more and more higher; In addition, in industries such as high-purity phosphoric acid, semi-conductor, petrochemical industry and automobile makings, the purity of yellow phosphorus is required also more and more higher.
At present, there is the Yellow phosphorus arsenic removing technique of report to have both at home and abroad and how to plant very much, be summed up and can be divided into physics method, chemical method and additive method. In prior art, chemical water phase oxidation is a kind of comparatively economic, safe arsenic removing method.
Existing document discloses some aqueous-phase oxidation method dearsenicating methods:
Japanese Patent JPS5493692A, nitric acid or sulfuric acid and mixture thereof is adopted to be oxygenant, aqueous phase acid concentration is 20%-50%, but the method has a large amount of phosphorus oxidized and loses, produce the mixed acid waste liquors such as a large amount of phosphoric acid, nitric acid or sulfuric acid simultaneously, also can produce a large amount of acid waste gas containing oxynitride in process of production
Chinese patent CN102107859A, adopts charcoal absorption associating dust technology washing purifying yellow phosphorus, and dust technology concentration is 8%-15%, and the method can produce to contain the waste liquid of the acid waste gas of a large amount of nitrogen-containing oxide and phosphoric acid, nitric acid nitration mixture when nitric acid wash; Meanwhile, when using charcoal absorption to filter, due to the adsorption of gac, part yellow phosphorus is attracted to activated carbon surface and defines the mud phosphorus containing element phosphor, causes the deadweight loss of yellow phosphorus; When the mixture after charcoal absorption yellow phosphorus being carried out deionized water and washes, a large amount of washing sewage will be produced.
Chinese patent CN1962420A, adopt in liquid-state industrial yellow phosphorus quiescent settling after the carbonate agitator treating adding 8%-15% industrial yellow phosphorus weight, then stirring containing concentration of nitric acid 15%-18% and yellow phosphorus weight 10%-40% of yellow phosphorus weight 150%-200% is put into containing the mixing solutions of iodine concentration 6-10%, add active carbon powder agitation and filtration afterwards again and obtain finished product, can find out that the dearsenification reagent type that the method uses is more from describe, have acid, alkali to also have gac etc., thus its method flow longer, operate loaded down with trivial details;The acid waste gas of a large amount of nitrogen-containing oxide can be produced when adopting nitric acid and process containing iodine compound and contain the mixed waste liquor of nitric acid, iodine compound, phosphoric acid; Produce a large amount of mud phosphorus containing element phosphor when utilizing charcoal absorption, cause the deadweight loss of yellow phosphorus so that production cost is higher, and water washing process creates massive laundering waste water; Meanwhile, what adopt high value contains iodine compound as dearsenification reagent, further increases production cost.
Chinese patent CN1257040, adopting the compound containing halogen element to add dust technology is liquid-phase oxidation agent process yellow phosphorus, and the method halogenide addition is big, treatment solution and yellow phosphorus weight ratio are also relatively big, about 4-5 times, comparatively speaking, the loss of the method phosphorus is relatively big, and the extrusion rate of arsenic is limited; The method can produce the acid waste gas of a large amount of nitrogen-containing oxide when processing, and also can produce the waste liquid containing nitric acid, halogenide and a small amount of phosphoric acid.
Chinese patent CN1311756A, adopts the enough oxyiodide process sufficiently long time, reaches the object reducing arsenic content. The method has good arsenic extrusion rate, also can take off except antimony simultaneously, but the method can produce the waste liquid containing iodine, arsenic and a small amount of phosphoric acid, is dearsenification reagent owing to employing the oxyiodide of high value simultaneously, and thus the method production cost is higher.
In sum, aqueous phase oxidation dearsenicating method in prior art, difference according to selected oxygenant, it is not obvious to there is removal effect in the reasons such as the dearsenic agent owing to using is expensive, phosphorus loss is relatively big, dearsenification process flow is loaded down with trivial details compared with farm labourer's skill, production cost height, poor safety performance, the problems such as purity is low.
Summary of the invention
The present invention is in order to overcome the deficiencies in the prior art, it provides one can efficiently dearsenification, the method for the Yellow phosphorus arsenic removing of safety economy.
The technical solution used in the present invention is as follows:
The method of a kind of yellow phosphorus oxidation arsenic removal, at ambient pressure, mix the yellow phosphorus under dearsenic agent solution and molten state to interact, arsenic in yellow phosphorus is oxidized to solubility arsenide enter aqueous phase and take off and remove, wherein mix dearsenic agent solution and comprise basis oxygenant, oxide catalyst and enhancing oxygenant, namely obtaining dearsenification yellow phosphorus finally by ultrapure water after repeatedly washing, concrete operation steps is as follows:
(1) charging heating: oxygenant based on preparation salpeter solution, drops into yellow phosphorus by a certain percentage in the reactor that basis oxygenant is housed and stirs, and Homogeneous phase mixing, heats and keep temperature;
(2) oxide catalyst is added: adding oxide catalyst after 10 ~ 60min that yellow phosphorus and basis oxygenant are uniformly mixed, wherein oxide catalyst is liquor kalii iodide;
(3) adding oxidation toughener: add once oxidation toughener in reactor every 40 ~ 60min after adding oxide catalyst, being wherein oxidized toughener is hydrogen peroxide solution;
(4) wash: yellow phosphorus is delivered in washing bath after terminating by reaction, carry out 2 ~ 3 washings with 65 ~ 80 DEG C of hot water, until water lotion is in neutral, obtain dearsenification yellow phosphorus.
Heating and temperature control in above-described step (1) is 65 ~ 80 DEG C.
Certain proportion described in above step (1) is the weight ratio of salpeter solution and yellow phosphorus is 1 ~ 5:1.
Above-described oxide catalyst is the 1 ~ 5% of yellow phosphorus quality; Described oxidation toughener is the 5 ~ 20% of yellow phosphorus quality.
The mass concentration of above-described salpeter solution is 5 ~ 25%; The mass concentration of described liquor kalii iodide is 5 ~ 25%; The mass concentration of described hydrogen peroxide effective content is 10 ~ 30%.
Above-described oxidation toughener divides 2 ~ 4 times and adds.
In above-described step (4), after washing terminates, wash again after leaving standstill 5 ~ 10min next time.
Hot water in above-described step (4) is hot ultrapure water; Wash the washing of water lotion for the last time of discharge next time, first time washing terminate after water lotion deliver to Waste Water Treatment and do harmless treatment.
Compared to prior art, the present invention has the following advantages and positively effect:
1, adopting the present invention, in the reaction, under mixing dearsenic agent effect, yellow phosphorus forms good emulsifying particulate state, considerably increases the contact area of dearsenic agent and yellow phosphorus, promotes the carrying out of dearsenification reaction.
2, the present invention adopts segmentation repeatedly to add the mode of oxidation toughener hydrogen peroxide, ensure persistence and the high efficiency of whole dearsenification process dearsenification effect, in reaction process, it is oxidized the micro-bubble that toughener decomposing hydrogen dioxide solution becomes a large amount of simultaneously, too increases solid-liquid contact face; Catalyzer in mixing dearsenic agent makes dearsenification reaction more rapidly and efficiently carry out, and ensure that the high receipts rate simultaneously achieving yellow phosphorus of efficient dearsenification.
3, the abundant hot ultrapure water of the present invention is washed, and recycle, keep the quantity discharged simultaneously reducing waste water of yellow phosphorus purity, decrease power consumption, environmentally safe, reduce production cost, it is a kind of efficient, safe, economic arsenic removing method, there is good economic benefit and social benefit.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of a kind of Yellow phosphorus arsenic removing of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1:
A method for yellow phosphorus oxidation arsenic removal, at ambient pressure, preparation mass concentration is oxygenant based on the salpeter solution of 5 ~ 25%, and the weight ratio that yellow phosphorus and salpeter solution are pressed 1:1-5 drops into stirring in reactor, and Homogeneous phase mixing, heats and keep temperature to be 65 ~ 80 DEG C. Adding mass concentration after 10 ~ 60min that yellow phosphorus and basis oxygenant salpeter solution are uniformly mixed is 5 ~ 25% oxide catalyst liquor kalii iodides, and oxide catalyst liquor kalii iodide is the 1 ~ 5% of yellow phosphorus quality. The mass concentration adding a hydrogen peroxide effective content in reactor every 40 ~ 60min after adding oxide catalyst liquor kalii iodide is the oxidation toughener hydrogen peroxide solution of 10 ~ 30%, oxidation toughener hydrogen peroxide solution is the 5 ~ 20% of yellow phosphorus quality, divides and adds for 2 ~ 4 times.
Yellow phosphorus is delivered in washing bath after terminating by reaction, with the hot ultrapure waters of 65 ~ 80 DEG C, yellow phosphorus carries out 2 ~ 3 washings, first time washing terminate after water lotion deliver to Waste Water Treatment and do and harmless manage everywhere, carry out second time after leaving standstill 5-10min and wash; The water lotion that second time washing is discharged with the washing continuing on for first time, can be analogized with this, need standing 5-10min between every twice water-washing step, wash the washing of water lotion for the last time of discharge next time, recycle water lotion, until rinsing liquid is in neutral, obtains dearsenification yellow phosphorus.
Embodiment 2:
A method for yellow phosphorus oxidation arsenic removal, at ambient pressure, preparation mass concentration is oxygenant based on the salpeter solution of 10%, and the weight ratio that yellow phosphorus and salpeter solution are pressed 1:2 drops into stirring in reactor, and Homogeneous phase mixing, heats and keep temperature to be 70 DEG C. Adding mass concentration after the 40min that yellow phosphorus and basis oxygenant salpeter solution are uniformly mixed is 10% oxide catalyst liquor kalii iodide, and oxide catalyst liquor kalii iodide is the 2% of yellow phosphorus quality.The mass concentration adding a hydrogen peroxide effective content in reactor every 40min after adding oxide catalyst liquor kalii iodide is the oxidation toughener hydrogen peroxide solution of 10%, and oxidation toughener hydrogen peroxide solution is the 5% of yellow phosphorus quality, point adds for 4 times.
Yellow phosphorus is delivered in washing bath after terminating by reaction, with the hot ultrapure waters of 70 DEG C, yellow phosphorus carries out 2 washings, first time washing terminate after water lotion deliver to Waste Water Treatment and do and harmless manage everywhere, carry out second time after leaving standstill 5min and wash; The water lotion that second time washing is discharged with the washing continuing on for first time, can be analogized with this, need standing 5min between every twice water-washing step, wash the washing of water lotion for the last time of discharge next time, recycle water lotion, until rinsing liquid is in neutral, obtains dearsenification yellow phosphorus.
Embodiment 3:
A method for yellow phosphorus oxidation arsenic removal, at ambient pressure, preparation mass concentration is oxygenant based on the salpeter solution of 15%, and the weight ratio that yellow phosphorus and salpeter solution are pressed 1:3 drops into stirring in reactor, and Homogeneous phase mixing, heats and keep temperature to be 75 DEG C. Adding mass concentration after the 30min that yellow phosphorus and basis oxygenant salpeter solution are uniformly mixed is 15% oxide catalyst liquor kalii iodide, and oxide catalyst liquor kalii iodide is the 3% of yellow phosphorus quality. The mass concentration adding a hydrogen peroxide effective content in reactor every 45min after adding oxide catalyst liquor kalii iodide is the oxidation toughener hydrogen peroxide solution of 15%, and oxidation toughener hydrogen peroxide solution is the 15% of yellow phosphorus quality, point adds for 3 times.
Yellow phosphorus is delivered in washing bath after terminating by reaction, with the hot ultrapure waters of 75 DEG C, yellow phosphorus carries out 3 washings, first time washing terminate after water lotion deliver to Waste Water Treatment and do and harmless manage everywhere, carry out second time after leaving standstill 8min and wash; The water lotion that second time washing is discharged with the washing continuing on for first time, can be analogized with this, need standing 8min between every twice water-washing step, wash the washing of water lotion for the last time of discharge next time, recycle water lotion, until rinsing liquid is in neutral, obtains dearsenification yellow phosphorus.
Embodiment 4:
A method for yellow phosphorus oxidation arsenic removal, at ambient pressure, preparation mass concentration is oxygenant based on the salpeter solution of 20%, and the weight ratio that yellow phosphorus and salpeter solution are pressed 1:4 drops into stirring in reactor, and Homogeneous phase mixing, heats and keep temperature to be 80 DEG C. Adding mass concentration after the 20min that yellow phosphorus and basis oxygenant salpeter solution are uniformly mixed is 20% oxide catalyst liquor kalii iodide, and oxide catalyst liquor kalii iodide is the 4% of yellow phosphorus quality. The mass concentration adding a hydrogen peroxide effective content in reactor every 50min after adding oxide catalyst liquor kalii iodide is the oxidation toughener hydrogen peroxide solution of 25%, and oxidation toughener hydrogen peroxide solution is the 20% of yellow phosphorus quality, point adds for 2 times.
Yellow phosphorus is delivered in washing bath after terminating by reaction, with the hot ultrapure waters of 80 DEG C, yellow phosphorus carries out 2 ~ 3 washings, first time washing terminate after water lotion deliver to Waste Water Treatment and do and harmless manage everywhere, carry out second time after leaving standstill 8min and wash; The water lotion that second time washing is discharged with the washing continuing on for first time, can be analogized with this, need standing 8min between every twice water-washing step, wash the washing of water lotion for the last time of discharge next time, recycle water lotion, until rinsing liquid is in neutral, obtains dearsenification yellow phosphorus.
Embodiment 5:
A method for yellow phosphorus oxidation arsenic removal, at ambient pressure, preparation mass concentration is oxygenant based on the salpeter solution of 25%, and the weight ratio that yellow phosphorus and salpeter solution are pressed 1:5 drops into stirring in reactor, and Homogeneous phase mixing, heats and keep temperature to be 80 DEG C.Adding mass concentration after the 10min that yellow phosphorus and basis oxygenant salpeter solution are uniformly mixed is 25% oxide catalyst liquor kalii iodide, and oxide catalyst liquor kalii iodide is the 5% of yellow phosphorus quality. The mass concentration adding a hydrogen peroxide effective content in reactor every 60min after adding oxide catalyst liquor kalii iodide is the oxidation toughener hydrogen peroxide solution of 10 ~ 30%, and oxidation toughener hydrogen peroxide solution is the 20% of yellow phosphorus quality, point adds for 2 times.
Yellow phosphorus is delivered in washing bath after terminating by reaction, with the hot ultrapure waters of 80 DEG C, yellow phosphorus carries out 3 washings, first time washing terminate after water lotion deliver to Waste Water Treatment and do and harmless manage everywhere, carry out second time after leaving standstill 10min and wash; The water lotion that second time washing is discharged with the washing continuing on for first time, can be analogized with this, need standing 10min between every twice water-washing step, wash the washing of water lotion for the last time of discharge next time, recycle water lotion, until rinsing liquid is in neutral, obtains dearsenification yellow phosphorus.
Claims (4)
1. the method for a yellow phosphorus oxidation arsenic removal, it is characterized in that: at ambient pressure, mix the yellow phosphorus under dearsenic agent solution and molten state to interact, arsenic in yellow phosphorus is oxidized to solubility arsenide enter aqueous phase and take off and remove, wherein mix dearsenic agent solution and comprise basis oxygenant, oxide catalyst and enhancing oxygenant, namely obtaining dearsenification yellow phosphorus finally by ultrapure water after repeatedly washing, concrete operation steps is as follows:
(1) charging heating: oxygenant based on preparation salpeter solution, drops into yellow phosphorus by a certain percentage in the reactor that basis oxygenant is housed and stirs, and Homogeneous phase mixing, heats and keep temperature; Heating and temperature control is 65 ~ 80 DEG C; Described certain proportion is the weight ratio of salpeter solution and yellow phosphorus is 1 ~ 5:1;
(2) oxide catalyst is added: adding oxide catalyst after 10 ~ 60min that yellow phosphorus and basis oxygenant are uniformly mixed, wherein oxide catalyst is liquor kalii iodide; Described oxide catalyst is the 1 ~ 5% of yellow phosphorus quality;
(3) adding oxidation toughener: add once oxidation toughener in reactor every 40 ~ 60min after adding oxide catalyst, being wherein oxidized toughener is hydrogen peroxide solution; Described oxidation toughener is the 5 ~ 20% of yellow phosphorus quality;
(4) wash: yellow phosphorus is delivered in washing bath after terminating by reaction, carry out 2 ~ 3 washings with 65 ~ 80 DEG C of hot water, until water lotion is in neutral, obtain dearsenification yellow phosphorus;
The mass concentration of described salpeter solution is 5 ~ 25%; The mass concentration of described liquor kalii iodide is 5 ~ 25%; The mass concentration of described hydrogen peroxide effective content is 10 ~ 30%.
2. the method for a kind of yellow phosphorus according to claim 1 oxidation arsenic removal, it is characterised in that: described oxidation toughener divides 2 ~ 4 times and adds.
3. the method for a kind of yellow phosphorus according to claim 1 oxidation arsenic removal, it is characterised in that: in described step (4), after washing terminates, wash again after leaving standstill 5 ~ 10min next time.
4. the method for a kind of yellow phosphorus according to claim 1 oxidation arsenic removal, it is characterised in that: the described hot water in step (4) is hot ultrapure water; Wash the washing of water lotion for the last time of discharge next time, first time washing terminate after water lotion deliver to Waste Water Treatment and do harmless treatment.
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| CN201310747146.8A CN103771366B (en) | 2013-12-30 | 2013-12-30 | The method of a kind of yellow phosphorus oxidation arsenic removal |
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| CN103771366B true CN103771366B (en) | 2016-06-08 |
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| CN108910846B (en) * | 2018-06-26 | 2020-10-27 | 贵州微化科技有限公司 | Method for preparing low-arsenic yellow phosphorus by using microchannel reactor |
| CN109607501B (en) * | 2019-01-16 | 2021-01-15 | 中州新材料(杭州)有限公司 | Yellow phosphorus purification process |
| CN111533097A (en) * | 2019-10-30 | 2020-08-14 | 贵州新天鑫化工有限公司 | Yellow phosphorus oxidation dearsenification method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4664896A (en) * | 1983-11-14 | 1987-05-12 | Fmc Corporation | Process for purifying yellow phosphorus |
| CN1257040A (en) * | 1998-12-15 | 2000-06-21 | 云南工业大学 | Method for making low-arsenic yellow phosphorus |
| CN1311756A (en) * | 1998-06-05 | 2001-09-05 | Fmc有限公司 | Process for removing arsenic from elemental phosphorus |
| CN101045532A (en) * | 2007-04-30 | 2007-10-03 | 贵阳精一科技有限公司 | Production of electronic grade yellow phosphorus |
| CN102336398A (en) * | 2010-07-09 | 2012-02-01 | 日本化学工业株式会社 | Method for production of high purity elemental phosphorus and method for production of high purity phosphoric acid |
-
2013
- 2013-12-30 CN CN201310747146.8A patent/CN103771366B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4664896A (en) * | 1983-11-14 | 1987-05-12 | Fmc Corporation | Process for purifying yellow phosphorus |
| CN1311756A (en) * | 1998-06-05 | 2001-09-05 | Fmc有限公司 | Process for removing arsenic from elemental phosphorus |
| CN1257040A (en) * | 1998-12-15 | 2000-06-21 | 云南工业大学 | Method for making low-arsenic yellow phosphorus |
| CN101045532A (en) * | 2007-04-30 | 2007-10-03 | 贵阳精一科技有限公司 | Production of electronic grade yellow phosphorus |
| CN102336398A (en) * | 2010-07-09 | 2012-02-01 | 日本化学工业株式会社 | Method for production of high purity elemental phosphorus and method for production of high purity phosphoric acid |
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