CN1265373A - Yellow phosphorus de-oiling and dearsenicating method - Google Patents
Yellow phosphorus de-oiling and dearsenicating method Download PDFInfo
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- CN1265373A CN1265373A CN 00112691 CN00112691A CN1265373A CN 1265373 A CN1265373 A CN 1265373A CN 00112691 CN00112691 CN 00112691 CN 00112691 A CN00112691 A CN 00112691A CN 1265373 A CN1265373 A CN 1265373A
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Abstract
The de-oiling and dearsenicating method of the present invention includes the compleation and chelation of ionic arsenic in yellow phosphorus; the extraction and separation of arsenic complex and chelate as well as gummy oils impurity; arsenic compound eliminating process and control parameters. The method can result in dearsenicating rate up to 90%, deoiling rate up to 95%, phosphorus content in the product up to 99.98% and phosphorus loss less than 3%, so that it is suitable for production of low-arsenic, low-gummy oil and high-purity yellow phosphorus.
Description
The invention relates to a process method for deoiling and removing arsenic from yellow phosphorus.
The existing method for removing arsenic from yellow phosphorus at home and abroad is as follows:
1. the method for removing arsenic from the selected phosphate ore comprises the following steps: the method is to select the raw material of the phosphorus ore used in the electric furnace to produce the yellow phosphorus, and remove the arsenic-containing minerals carried in or symbiotic with the phosphorus ore, so as to achieve the purpose of reducing the arsenic content of the yellow phosphorus product. The method has low arsenic removal rate, generally 30-40%, can not remove the colloid oil, and has large equipment investment and high beneficiation cost.
2. Removing arsenic by a nitric acid method: the method comprises the steps of mixing and reacting an aqueous solution containing 10-50% of nitric acid with yellow phosphorus at 70-90 ℃, oxidizing arsenic in the yellow phosphorus into arsenous acid or arsenic acid, dissolving the arsenous acid or arsenic acid in the aqueous phase, standing and layering, and obtaining the low-arsenic yellow phosphorus as the bottom layer yellow phosphorus. The method is dangerous in production, explosion accidents easily occur due to heat release of oxidation reaction (1 death caused by explosion of the method in three years of tests in Yunnan province), and phosphorus is oxidized into phosphoric acid while oxidation is carried out, so that more elemental phosphorus is lost.
3. And (3) removing arsenic by a distillation method: the method is characterized in that the property that the boiling point of phosphorus is lower than that of arsenic is utilized, yellow phosphorus is put into a distillation kettle, steam is used for stripping the yellow phosphorus, and the yellow phosphorus steam is cooled by hot water to obtain the low-arsenic yellow phosphorus. The method has the defects of large heat energy consumption, low arsenic removal rate, high production cost and incapability of removing the colloid oil, so that no application manufacturer exists in China.
The invention aims to overcome the defects of the existing arsenic removal and deoiling method, change the backward situation that no low-arsenic, low-oil and high-purity yellow phosphorus products are produced in batches in China, promote the conversion of the yellow phosphorus products in China from low-quality raw material types to high-quality high-purity benefit types, and meet the strict requirements of the electronic industry, the food industry and the pharmaceutical industry on the quality of the yellow phosphorus products.
The content of the invention is as follows: selecting carbon tetrachloride or chloroform as an extraction solvent; selecting EDTA and sodium salt as complexing agent of ion arsenic; selecting DDTC-X as a chelating agent of arsenic ions; stirring and mixing high-arsenic yellow phosphorus, process water, an extraction solvent, a quantitative complexing agent and a chelating agent for reaction under the conditions that the pH value is 4-6 and the temperature is 50-70 ℃, so that ion arsenic in the yellow phosphorus forms arsenic complex and arsenic chelate to enter the extraction solution, and colloid oil in the yellow phosphorus also enters the extraction solvent. Standing for layering, and recycling the upper-layer aqueous solution; after the complex arsenic, the chelated arsenic and the gum oil contained in the middle-layer organic phase are basically saturated, rinsing and back-extracting the organic phase by using a dilute alkali aqueous solution containing 3-10% of (NaOH) so that the complex arsenic, the chelated arsenic and the gum oil are transferred into the dilute alkali aqueous solution, and recycling the extraction solvent for extracting the arsenic; the yellow phosphorus at the bottom layer is a medium-grade low-arsenic low-gum oil yellow phosphorus product. In order to produce yellow phosphorus with high purity and lower arsenic, simple substance zinc particles (powder) and an aqueous solution containing 2-10% of hydrogen chloride are selected to perform arsenic removal treatment on the extracted medium-grade low-arsenic yellow phosphorus again at the temperature of 50-70 ℃; converting arsenic phosphide in yellow phosphorus into arsine gas, and absorbing A with dilute alkali water solutionSH3And processing to obtain high-purity low-arsenic low-gum-oil yellow phosphorus product, washing the product with deionized hot water, weighing and packaging to obtain the finished product.
Description of the drawings: DDTC-X represents: zinc diethyldithiocarbamate (C)5H10NS2Zn) Sodium diethyldithiocarbamate (C)5H10NNaS2) Tetramethylthiuram disulfide (C)6H12N2S4) Tetraethylthiuram disulfide(C10H20N2S4) Sodium diethylthiocarbamate (C)4H10NOSSNa) An organic sulfide; EDTA means ethylenediaminetetraacetic acid or disodium ethylenediaminetetraacetate.
The chemical principle of the invention is as follows:
1.
2.
3.
4.
the control parameters of the invention are as follows:
the adding amount of the extraction solvent is 20-50% of the weight of the yellow phosphorus; the addition amount of the DDTC-X is 0.02-0.1% of the weight of the yellow phosphorus; the addition amount of the EDTA and the sodium salt is 0.01-0.05% of the weight of the yellow phosphorus; the adding amount of the zinc powder is 0.08-0.2% of the weight of the yellow phosphorus; temperature control: 50-70 ℃; reacting a hydrochloric acid aqueous solution with zinc powder to control the content of hydrogen chloride to be 2-10%; concentration of dilute alkali aqueous solution for back extraction and arsine absorption: 3-10%; DDTC-X can be used alone or in combination of several.
Theprocess flow diagram of the invention is shown in the attached drawing of the specification.
Compared with the prior art, the method has the characteristics of less equipment investment, high production efficiency, simple operation and control, safe and reliable production, convenient production of low-arsenic and low-gum oil yellow phosphorus products with different grades, less energy consumption, low production cost and low phosphorus loss rate. By implementing the invention, the arsenic removal rate can reach 90%, the oil removal rate can reach 95%, the phosphorus content of the product can reach 99.98%, the phosphorus loss rate is less than 3%, and the economic benefit is very obvious. The production cost and benefit are approximated as follows:
1. the production cost is as follows: 274 Yuan/+ (dearsenic agent: 1 Kg 30 Yuan/Kg 30 Yuan; hydrochloric acid: 30 Kg 0.8 Yuan/Kg 24 Yuan; zinc powder: 1.5 Kg 20 Yuan/Kg 30 Yuan; electricity: 10 degree X1 Yuan/degree 10 Yuan; labor cost: 30 Yuan; other unforeseeable cost: 150 Yuan)
2. Selling price of the product: 11000 yuan/t (introduced by Zhao Shi Chi of Jiangxuan phosphorization company in Yunnan province: yellow phosphorus with arsenic less than 0.002% is sold at the price of 20000 yuan/t, yellow phosphorus with arsenic less than 0.005% is sold at the price of 15000 yuan/t, yellow phosphorus with arsenic less than 0.008% is sold at the price of 12000 yuan/t, and yellow phosphorus with arsenic less than 0.01% is sold at the price of 9000 yuan/t).
The average selling price is calculated according to 11000 yuan/t, and the selling price of the common industrial yellow phosphorus is calculated according to 8000 yuan/t.
3. The profit of each ton of product is 11000 Yuan-274 Yuan-8000 Yuan-500 Yuan (value-added tax) 2330 Yuan/t
4. 2000 ton annual profit 2000t × 2330 yuan/t 466 ten thousand yuan/year
Example (b):
volume of 1.2M3The first arsenic removal tower is filled with process water and heated by introducing steam, and the temperature in the tower is controlled to be 60 +/-5 ℃; regulating the pH value of the aqueous solution in the tower to be 5 by using hydrochloric acid; pressing 1000 kg of melted high arsenic yellow phosphorus into the tower; pressing 400 kg of carbon tetrachloride into the tower; adding 200 g of disodium ethylene diamine tetraacetate into the tower; adding 200 g of zinc diethyldithiocarbamate; adding 300 g of sodium dimethyldithiocarbamate; 200 g of tetramethyl thiuram disulfide; and when feeding, discharging redundant process water in the tower into a process hot water storage tank through an overflow pipe at the top of the tower for storage for later use. And after the feeding is finished, respectively pumping out the organic extraction solvent in the middle layer and the water phase in the upper layer in the tower by a boiled water circulating pump and an extraction solvent circulating pump, pressing the organic extraction solvent and the water phase in the upper layer into the tower from the bottom of the tower, fully stirring, mixing and reacting the water layer, the organic layer and the phosphorus layer in the tower for 30 minutes, stopping the circulating pump, standing for 20 minutes, adding process hot water from the upper part of the tower, and pressing the yellow phosphorus in the bottom layer into a second arsenic removal tower. After the phosphorus is discharged, the pressure water pump and the phosphorus discharge valve are closed, the overflow valve and the phosphorus adding valve at the top of the tower are opened, high-arsenic yellow phosphorus is pressed into the tower, a complexing agent and a chelating agent are added, the pH value is adjusted, and then the next round of extraction and arsenic removal is carried out. When the arsenic and the glue oil in the extraction solvent are basically saturatedAnd or when the arsenic removal agent is used for 5-10 periods, putting the organic phase in the tower into a back extraction device, rinsing the organic phase with aqueous solution containing 5% of NaOH for 30 minutes, standing and layering, regenerating the bottom-layer extracting agent, circulating the extracting agent into the first arsenic removal tower for use, adding lime into the upper-layer aqueous solution to precipitate arsenic compounds, and performing post-treatment.
The volume of the second arsenic removing tower is 1.2M3Adding process hot water containing 3% of hydrogen chloride in advance, controlling the temperature in the tower to be 50-70 ℃, and pressing 1000 kilograms of yellow phosphorus to be subjected to arsenic removal into the tower. And (4) discharging the excessive water in the tower into a second hot water storage tank through an overflow pipe at the top of the tower for storage for later use due to the addition of the yellow phosphorus. After the phosphorus is added, the arsenic hydride gas guide valve at the top of the tower is opened to lead the arsenic generated in the tower to be changedIntroducing the hydrogen gas into an absorption tower, and circularly spraying and absorbing by using dilute alkali liquor containing 5 percent of NaOH (caustic soda). After the absorption device normally operates, 1000 g of zinc particles (powder) are added into the second arsenic removal tower; and starting a circulating stirring pump, pumping the upper acid-containing aqueous solution in the tower, pressing the upper acid-containing aqueous solution in the tower from the bottom of the tower, and circularly stirring for 40 minutes to fully mix and contact the water layer, the phosphorus layer and the zinc particles in the tower. And after the reaction is finished, stopping the circulating stirring pump, standing for 20 minutes, pressing in process hot water in a second hot water storage tank from the upper part of the tower, pressing out the yellow phosphorus at the bottom layer into hot water in a hot water rinsing tower, controlling the water temperature in the rinsing tower to be 50-80 ℃, circularly rinsing for 20 minutes by using deionized hot water at the corresponding temperature, standing for layering, sampling and checking the yellow phosphorus at the bottom layer of the rinsing tower, pressing into a packaging barrel, weighing and packaging to obtain the low-arsenic yellow phosphorus product. If the arsenic content is detected to be higher, the yellow phosphorus at the bottom layer of the rinsing tower is pressed into the first arsenic removal tower or the second arsenic removal tower, and then arsenic removal treatment is carried out. When the content of hydrogen chloride in the aqueous solution in the second hot water storage tank is lower than 2%, adding hydrochloric acid, and maintaining the content of HCl to be 2-10%; when the solution in the storage tank contains about 30% of zinc chloride, ammonium bicarbonate can be added to react with the solution, and the zinc carbonate product is precipitated and recovered; the solution after zinc recovery can be discharged as a nitrogen fertilizer; after discharging, adding hot water and hydrochloric acid again, and adjusting the content of HCl.
Claims (1)
1. A method for deoiling and removing arsenic from yellow phosphorus comprises the steps of complexing and chelating ion arsenic in yellow phosphorus, complexing arsenic, chelating arsenic, extracting and separating gum oil, removing and separating combined arsenic in yellow phosphorus, operating procedures and process control parameters; the method is characterized in that:
extracting ion arsenic and gum oil in yellow phosphorus by using carbon tetrachloride or chloroform as an extraction solvent, EDTA (ethylene diamine tetraacetic acid) and disodium salt as complexing agents and DDTC-X as a chelating agent under the conditions of a pH value of 4-6 and a temperature of 50-70 ℃, and back-extracting by using dilute alkali liquor to regenerate and recycle the extraction solvent; converting the combined arsenic in the yellow phosphorus into arsine gas and separating and absorbing the arsine gas in the presence of zinc powder at the temperature of 50-70 ℃ and the hydrogen chloride content of 2-10% in an aqueous solution; the adding amount of the extraction solvent is 20-50% of the weight of the yellow phosphorus; the addition amount of the DDTC-X is 0.02-0.1% of the weight of the yellow phosphorus; the addition amount of the EDTA and the sodium salt is 0.01-0.05% of the weight of the yellow phosphorus; the adding amount of the zinc powder is 0.08-0.2% of the weight of the yellow phosphorus.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00112691 CN1265373A (en) | 2000-02-18 | 2000-02-18 | Yellow phosphorus de-oiling and dearsenicating method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 00112691 CN1265373A (en) | 2000-02-18 | 2000-02-18 | Yellow phosphorus de-oiling and dearsenicating method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100510706C (en) * | 2005-11-08 | 2009-07-08 | 白莉 | Arsenic assaying liquid and colorimetric cylinder thereof |
| 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 |
| CN111517296A (en) * | 2020-05-22 | 2020-08-11 | 四川君和环保股份有限公司 | Method for recovering yellow phosphorus from phosphorus-containing sludge by utilizing trichloromethane |
-
2000
- 2000-02-18 CN CN 00112691 patent/CN1265373A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100510706C (en) * | 2005-11-08 | 2009-07-08 | 白莉 | Arsenic assaying liquid and colorimetric cylinder thereof |
| 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 |
| CN102336398B (en) * | 2010-07-09 | 2016-08-10 | 日本化学工业株式会社 | The manufacture method of high purity elements phosphorus |
| CN111517296A (en) * | 2020-05-22 | 2020-08-11 | 四川君和环保股份有限公司 | Method for recovering yellow phosphorus from phosphorus-containing sludge by utilizing trichloromethane |
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