CN103588185B - Yellow phosphorus sulfur method - Google Patents
Yellow phosphorus sulfur method Download PDFInfo
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- CN103588185B CN103588185B CN201310564972.9A CN201310564972A CN103588185B CN 103588185 B CN103588185 B CN 103588185B CN 201310564972 A CN201310564972 A CN 201310564972A CN 103588185 B CN103588185 B CN 103588185B
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Abstract
A kind of yellow phosphorus sulfur method, adopts the certain density solubility organic amine aqueous solution to be fully uniformly mixed as sweetening agent and yellow phosphorus, makes sulfur-containing impurities enter the aqueous solution, thus realizes and yellow phosphorus separation removal.Organic amine can select alkyl tertiary amine class, alcamines, amides, quaternary ammonium salt, polynary amine etc. to have water miscible organic amine, amine salt.The method has that flow process is short, manipulation is convenient, high, safe without gas-solid contaminant exclusion, yellow phosphorus yield, easily realize the features such as industrialization.
Description
Technical field
The present invention relates to yellow phosphorus intensive processing field in sulphur dioxide of phosphor chemical industry, particularly the removal methods of sulfur impurity in a kind of industrial yellow phosphorus process for refining.
Background technology
Yellow phosphorus is one of phosphorous chemical industry basic material, is almost the raw material of all fine phosphorus chemical products.Yellow phosphorus, as in the use procedure of fine phosphorus chemical basic material, has comparatively strict requirement to foreign matter contents such as arsenic wherein, sulphur.In recent years, along with China's rapid development of economy, the consumption of coal resources constantly increases, the dilution of coal resources quality aggravates, a large amount of high-sulfur coal is applied to the production of coke, cause sulphur content in coke constantly to rise, cause sulphur content in electric furnace process yellow phosphorus product also in continuous rising thus, make yellow phosphorus product application scope receive larger restriction.Therefore, carrying out yellow phosphorus purification desulfurization technology has been extremely urgent.
At present, the yellow phosphorus sulfur removal technology research of report mainly contains chemical method and absorption method both at home and abroad.Chemical method mainly adopts chemical agent to process yellow phosphorus sulfur impurity is wherein removed from yellow phosphorus, absorption method mainly adopts the sorbent materials such as the gac with stronger adsorptive power and large surface area, utilizes it to make sulfur impurity be separated from yellow phosphorus, remove to the characteristic of yellow phosphorus, sulfur impurity adsorptive power difference.
Existing document discloses the method for some yellow phosphorus desulfurization:
Chinese patent: publication number CN1073659, application number: 91111846.2), in yellow phosphorus molten mass, add specific surface area be less than 800 meters
2/ gram powdered active carbon, mix under turbulence state, its time length should be enough to make it contact, and generated suspension is separated into purification phosphorus and solid sediment.The method solid sediment and yellow phosphorus sepn process have higher danger and process cost, obtain mud phosphorus need carry out harmless treatment, add cost.Due to the adsorption of gac when the method is owing to using charcoal absorption to filter, part yellow phosphorus is attracted to activated carbon surface and defines mud phosphorus containing element phosphor namely containing the mixture of element phosphor and solids, causes the deadweight loss of yellow phosphorus.
Chinese patent: publication number: CN101045532: title: a kind of production method of electronic grade yellow phosphorus, industrial yellow phosphorus is put into the container filling oxidisability strong acid and pure water mixed solution by the method, heat and stir, when temperature is raised to 75 ~ 85 DEG C, add oxidisability strong acid and add reductive agent, oxidation toughener and tensio-active agent, heat and stir, pump supernatant liquid, 2 ~ 4 times so repeatedly; Add non-oxidizing acid, water glass and pure water, heat and stir; Pump supernatant liquid, the pure water of reusable heat, heat and stir, until supernatant liquid is washed neutrality; And then add pure gac, heat and stir, filtering and obtain yellow phosphorus product.The method yellow phosphorus yield is about 80%, gives the purification sulphur content of yellow phosphorus but raw material yellow phosphorus sulphur content does not provide in embodiment, thus cannot judge the removal effect of sulfur impurity.Meanwhile, the reagent type that the method uses can be found out from description and quantity is more, flow process is longer, complex operation, can produce a large amount of acidic mixed waste liquid; Producing a large amount of mud phosphorus containing element phosphor when utilizing charcoal absorption, cause the deadweight loss of yellow phosphorus, make production cost higher, and rinse cycle creating a large amount of poaching wastewater.
Chinese patent: publication number: CN1565961, title: the production technique of electronic grade red phosphorus, adopt and technical grade yellow phosphorus is put into strong acid, add the reductive agent made of salt compounded of iodine and molysite, heating, stirring, then filter, add non-oxidizing acid in yellow phosphorus after filtering and add molysite and potassium permanganate, heat and stir rear filtration, the product obtained being put into container, adds gac, heat and stir rear filtration, wash to obtain the yellow phosphorus that processed with water, then put into by yellow phosphorus and transform pot, heating and adding rare gas element obtains electronic grade red phosphorus product.This method give the sulphur content of raw material yellow phosphorus and product red phosphorus, but the sulphur removal effect in yellow phosphorus purification process is not evaluated.The method flow process is longer, complex operation, can produce acidic mixed waste liquid; Producing a large amount of mud phosphorus containing element phosphor when utilizing charcoal absorption, cause the deadweight loss of yellow phosphorus, make production cost higher, and rinse cycle creating a large amount of poaching wastewater; Meanwhile, what adopt high value contains iodine compound as reagent treatment, further increases production cost.
German patent DE 76482: employing weight is that the vitriol oil of yellow phosphorus weight 15-18% is separated with yellow phosphorus the yellow phosphorus obtained compared with low sulfur concentration in special reactor after hybrid reaction; The method is diluted heat release due to fierceness in vitriol oil use procedure and is easily blasted, and adds operational danger; In addition, the method also creates a large amount of dilute sulphuric acid waste liquids; Although the method can remove the sulphur in part material yellow phosphorus, when processing, sulfuric acid can remain in yellow phosphorus, makes the method sweetening effectiveness not good.US Patent No. 5296212A adds the process to removing the rear residual sulfuric acid of purification on above-mentioned German Patent basis, enhances sweetening effectiveness, but still there is the shortcoming of aforesaid method operational hazards; Also large amount of sewage can be newly increased simultaneously.
Document " Xiong Xiangzu; Chen Lianyun. in industrial yellow phosphorus, Determination of Trace Sulfur removes [J]. the design of sulphur phosphorus and powder technology; 1996; (02) ": adopt carbon adsorbent, with adsorption method, the Determination of Trace Sulfur in industrial yellow phosphorus is removed, purified, have studied the impact of different parameters on adsorption desulfurize.The method and Chinese patent CN1073659A have higher similarity.
To sum up, above-mentioned yellow phosphorus sulfur method, exist or removal effect not obvious, or the shortcoming such as the higher costliness of sweetening agent used, phosphorus loss are comparatively large, sweetening process flow process is loaded down with trivial details compared with farm labourer's skill, operational hazards, aforesaid method major part fails to realize industrialization.
Summary of the invention
Technical problem to be solved by this invention proposes a kind of economic, yellow phosphorus purification sulfur method efficiently, adopts the method to obtain the lower yellow phosphorus of sulphur content, and the method has that flow process is short, manipulation is convenient, safety, easily realizes the features such as industrialization simultaneously.
The technical solution used in the present invention is: a kind of yellow phosphorus sulfur method, the method is at ambient pressure, concentration is adopted to be that the aqueous solution of one or more combination thing in the solubility alkyl tert amine of 0.01%-20%, alcamines, amides, quaternary ammonium salt, polynary amine organic amine is as sweetening agent, yellow phosphorus is put into after sweetening agent is fully uniformly mixed reaction certain hour and be separated and namely obtain the lower yellow phosphorus of sulphur content, wherein, the part by weight of sweetening agent and yellow phosphorus controls between 1:1-10:1, and temperature of reaction controls between 50 DEG C-85 DEG C.
Alkyl tert amine selection kind is: positive trihexylamine, triethylamine; Alcamines selection kind is: methyldiethanolamine, diisopropanolamine (DIPA), tri-isopropanolamine, diglycolamine, oleic acid diethanolamine, α-amino isopropyl alcohol, dimethyl diethanolamine, trolamine; Amides selection kind is: N,N-dimethylacetamide, N, N-di-alcohol amine hydroxybenzene, ethylene two amine hydroxybenzene, HMPA, dimethyl formamide, cocoanut fatty acid diethanolamide; Polynary amine selection kind is: triethylene tetramine, tetraethylene pentamine, quadrol; Quaternary ammonium salt selection kind is: tetramethyl ammonium chloride, tetrabutylammonium chloride, etamon chloride, three pungent ammonio methacrylates, distearyl dimethyl ammonium chloride; Amine salt selection kind is: tetrasodium ethylenediamine tetraacetate, ethanolamine hydrochloric salt.
In the present invention, the concentration of sweetening agent is the weight ratio of organic amine and water between 0.01-20%(), but 5-20% is better, and the best is 5-10%.Concentration is too low, and sulphur extrusion rate is lower; Otherwise excessive concentration, increases the loss of yellow phosphorus, too increases the consumption of sweetening agent simultaneously.
The weight ratio of sweetening agent and yellow phosphorus is 1:1-10:1, but preferably 1.5:1-8:1, be preferably 2:1-6:1.Sweetening agent and yellow phosphorus weight ratio large time desulfurization easy, and not easily there is yellow phosphorus and air catalytic combustion, cause the meaningless loss phenomenon of yellow phosphorus in sweetening process, and greatly, the waste liquid amount of generation is also more for the desulfurization dosage consumed in such cases; Otherwise the decreasing ratio of sulfur impurity reduces in yellow phosphorus.Be that 2:1-6:1 is comparatively suitable for the consideration sweetening agent of economy and the weight ratio of yellow phosphorus.Sweetening agent can disposablely before the reaction add, and also can add by substep in reaction process.
According to the present invention, temperature of reaction is 50-85 DEG C, but preferably 55-80 DEG C, be preferably 60-75 DEG C.When temperature is low, yellow phosphorus viscosity is high, and be unfavorable for yellow phosphorus dispersion in aqueous, in yellow phosphorus, the extrusion rate of sulphur is low; When temperature is too high, the less stable of sweetening agent, adds the unnecessary loss of sweetening agent.
This sweetening process is mutually insoluble two phase reaction process, the enforcement of sweetening process can at the reactor with two-phase mixtures function, carry out in the enamel reaction still of band agitating function conventional in such as Chemical Manufacture, also can carry out in the cylindrical reactor with stirring and heating function.Thus, the method both can be carried out in closed reactor, also can carry out in open reactor.
Based on the influence factor of above-mentioned sweetening process and the selection of reaction conditions, whole sweetening process flow process is short, manipulation convenient, high, safe without gas-solid contaminant exclusion, yellow phosphorus yield, easily realize industrialization.
Embodiment
Protection content of the present invention; described in detail by specific embodiment; for the specific preferred embodiment introduced in detail; just belong to an example in the scope defined in claims; only for specific example, claims four corner required for protection can not be represented.
In all embodiments, unless otherwise mentioned, all ratio is all weight ratio.
Yellow phosphorus desulfurization example all carries out in such as following reactor: desulphurization reactor is 12 liters of jacketeds heating cylindrical reactor, be furnished with adjustable speed whipping appts and reacting liquid temperature measuring apparatus, yellow phosphorus desulfurization reaction temperature regulates and carries out regulation and control by chuck hot water temperature.The analysis of sulphur content in yellow phosphorus: detect according to the sulfate radical detection method described in " GB/T2091-2008 industrial phosphoric acid " after phosphor sample nitric acid dissolve is oxidized to phosphoric acid.
embodiment 1-4:
By preparing desulfurization aqueous solution 6L described in table 1 in above-mentioned reactor, chuck passes into hot water, when water temperature reaches 55 DEG C, adding 3 kilograms of sulphur contents is the yellow phosphorus of 152ppm, regulates chuck heating water temperature to make reacting liquid temperature reach 70 DEG C, starts to stir, react 1 hour under maintenance 70 DEG C of conditions, stop stirring, sedimentation, remove bottom yellow phosphorus and detect, in final yellow phosphorus, sulphur content and yellow phosphorus yield are in table 1.
The desulfurization condition of table 1 embodiment 1-4 and result
Embodiment 5-8:
By preparing desulfurization aqueous solution 6L described in table 2 in above-mentioned reactor, chuck passes into hot water, when water temperature reaches 55 DEG C, adding 3 kilograms of sulphur contents is the yellow phosphorus of 152ppm, regulates chuck heating water temperature to make reacting liquid temperature reach 70 DEG C, starts to stir, react 1 hour under maintenance 70 DEG C of conditions, stop stirring, sedimentation, remove bottom yellow phosphorus and detect, in final yellow phosphorus, sulphur content and yellow phosphorus yield are in table 2.
The desulfurization condition of table 2 embodiment 5-8 and result
Embodiment 9-14:
By preparing desulfurization aqueous solution 6L described in table 3 in above-mentioned reactor, chuck passes into hot water, when water temperature reaches 55 DEG C, adding 3 kilograms of sulphur contents is the yellow phosphorus of 152ppm, regulates chuck heating water temperature to make reacting liquid temperature reach 70 DEG C, starts to stir, react 1 hour under maintenance 70 DEG C of conditions, stop stirring, sedimentation, remove bottom yellow phosphorus and detect, in final yellow phosphorus, sulphur content and yellow phosphorus yield are in table 4.
Table 3 mixed sweetening agent proportioning
The desulfurization condition of table 4 embodiment 9-14 and result
Claims (4)
1. yellow phosphorus sulfur method, it is characterized in that: at ambient pressure, concentration is adopted to be that the aqueous solution of one or more combination thing in the solubility alkyl tert amine of 0.01%-20%, alcamines, amides, quaternary ammonium salt, polynary amine organic amine is as sweetening agent, yellow phosphorus is put into after sweetening agent is fully uniformly mixed reaction certain hour and be separated and namely obtain the lower yellow phosphorus of sulphur content, wherein, the part by weight of sweetening agent and yellow phosphorus controls between 1:1-10:1, and temperature of reaction controls between 50 DEG C-85 DEG C.
2. yellow phosphorus sulfur method as claimed in claim 1, is characterized in that: alkyl tert amine selection kind is: positive trihexylamine, triethylamine; Alcamines selection kind is: methyldiethanolamine, diisopropanolamine (DIPA), tri-isopropanolamine, diglycolamine, oleic acid diethanolamine, α-amino isopropyl alcohol, dimethyl diethanolamine, trolamine; Amides selection kind is: N,N-dimethylacetamide, N, N-di-alcohol amine hydroxybenzene, ethylene two amine hydroxybenzene, HMPA, dimethyl formamide, cocoanut fatty acid diethanolamide; Polynary amine selection kind is: triethylene tetramine, tetraethylene pentamine, quadrol; Quaternary ammonium salt selection kind is: tetramethyl ammonium chloride, tetrabutylammonium chloride, etamon chloride, three pungent ammonio methacrylates, distearyl dimethyl ammonium chloride; Amine salt selection kind is: tetrasodium ethylenediamine tetraacetate, ethanolamine hydrochloric salt.
3. yellow phosphorus sulfur method as claimed in claim 1, it is characterized in that: sweetening agent concentration is 5%-10%, the part by weight of sweetening agent and yellow phosphorus is 2:1-6:1, and temperature of reaction is 60 DEG C-75 DEG C, and the reaction times is 0.5-2 hour.
4. yellow phosphorus sulfur method as claimed in claim 1, is characterized in that: the method is being opened wide or carried out in airtight reactor; In reaction process, sweetening agent once or step by step adds.
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| CN104147897A (en) * | 2014-07-21 | 2014-11-19 | 宜兴市星光宝亿化工有限公司 | DGA composite total sulfur removal agent used in petrochemical industry and preparation method of DGA composite total sulfur removal agent |
| CN109987593A (en) * | 2019-04-18 | 2019-07-09 | 舒爱桦 | A kind of friendly process of phosphorus mud recycling yellow phosphorus |
| CN110180329B (en) * | 2019-06-25 | 2022-02-25 | 中国石油大学(华东) | Novel benzene series volatile organic compound absorbent, preparation method and application thereof |
| CN113816348A (en) * | 2021-09-17 | 2021-12-21 | 贵州遄晴科技有限公司 | Low-temperature solid-liquid separation method for phosphorus sludge and medicament formula |
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| CA846695A (en) * | 1970-07-14 | Hartlapp Gerhard | Process for purifying yellow phosphorus and apparatus for carrying out the process on an industrial scale | |
| CN1073659A (en) * | 1991-12-23 | 1993-06-30 | 奎拜舍弗斯弗尔生产联合体 | The purifying method of yellow phosphorus |
| CN1532140A (en) * | 2003-03-20 | 2004-09-29 | 云南昆阳磷肥厂 | Method for producing high purity yellow phosphrus |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA846695A (en) * | 1970-07-14 | Hartlapp Gerhard | Process for purifying yellow phosphorus and apparatus for carrying out the process on an industrial scale | |
| CN1073659A (en) * | 1991-12-23 | 1993-06-30 | 奎拜舍弗斯弗尔生产联合体 | The purifying method of yellow phosphorus |
| CN1532140A (en) * | 2003-03-20 | 2004-09-29 | 云南昆阳磷肥厂 | Method for producing high purity yellow phosphrus |
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| "工业黄磷中微量硫的脱除";熊祥祖等;《硫磷设计》;19960430(第2期);第34-36页 * |
| "脱硫剂的研究进展";刘洋等;《当代化工》;20130630;第42卷(第6期);第827-829页 * |
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