CN104591100A - Method for preparing sulphuric acid from ardealite by membrane separation method - Google Patents
Method for preparing sulphuric acid from ardealite by membrane separation method Download PDFInfo
- Publication number
- CN104591100A CN104591100A CN201510019834.1A CN201510019834A CN104591100A CN 104591100 A CN104591100 A CN 104591100A CN 201510019834 A CN201510019834 A CN 201510019834A CN 104591100 A CN104591100 A CN 104591100A
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- China
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- membrane
- room
- membrane stack
- phosphogypsum
- sulfuric acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/745—Preparation from sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/02—Oxides or hydroxides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method for preparing sulphuric acid from ardealite by a membrane separation method. The method comprises the following steps: with regard to the current ardealite application status, by using ardealite as a raw material, separating industrial residue ardealite into sulphuric acid and calcium hydroxide through the membrane separation method, thus realizing the cyclic utilization of sulphuric acid in the phosphorus chemical industry, reducing the production cost, and laying a good foundation for the sustainable development of the phosphorus chemical industry. The method disclosed by the invention is simple and practicable, low in cost and good in use effect.
Description
Technical field
The present invention relates to a kind of method that industrial residue phosphogypsum prepares sulfuric acid, specifically a kind of membrane separation process utilizes phosphogypsum to prepare the method for sulfuric acid.
Background technology
China has about 8.3% of world phosphate resource, and resources occupation rate occupies third place in the world, and phosphorus ore and phosphate fertilizer production are the second in the world, simultaneously, China's P fertilizer consumption amount occupies the first in the world, accounts for about 29.7% of world's aggregate consumption, is one of phosphate fertilizer importer the biggest in the world.At present, in the middle of the method for phosphorous chemical industry production phosphoric acid, topmost method adopts wet production, namely utilizes sulfuric acid decomposition phosphorus ore, obtain primary product phosphoric acid and calcium sulfate.This calcium sulfate is called phosphogypsum.Often produce 1 ton of phosphoric acid, with 2.5 tons of vitriolization, 4 tons of phosphoric acid salt, 5 tons of phosphogypsums will be produced in this production process.Generally, phosphogypsum as industrial raw material, can produce cement or other material of construction, coproduction of ammonia sulfate and calcium carbonate, or make ammonium sulfate, potassium-ammonium sulfate, nitrogen-phosphorus-potassium compound fertilizer and calcium chloride etc., but owing to containing much impurity in phosphogypsum, affect its application.Therefore, the phosphogypsum solid waste of a large amount of discharge, brings obstacle to phosphorous chemical industry Sustainable development.
Summary of the invention
The object of the invention is: provide a kind of membrane separation process to utilize phosphogypsum to prepare the method for sulfuric acid, industrial residue phosphogypsum can be separated into sulfuric acid and calcium hydroxide by it, and technique is simple, with low cost, to overcome the deficiency that existing phosphogypsum utilizes technology.
The present invention is achieved in that membrane separation process utilizes phosphogypsum to prepare the method for sulfuric acid, comprises the steps:
1) phosphogypsum and water are ground pulping, be then diluted to that solid content is 4-20%, granularity is calcium sulfate emulsion between 0.3-10 μm, and calcium sulfate emulsion liquid is placed in membrane stack material liquid tank;
2) water is added to membrane stack acid room and membrane stack alkali room, in room, membrane stack pole, add sodium-chlor, Repone K or the potassium sulfate ionogen that mass concentration is 1%-20%, pass into direct supply respectively to room, two pole, control voltage is 5-50V, open the recycle pump of each room, Bipolar Membrane is worked under electric field action;
3) after 1-2h is carried out in reaction, after the calcium sulfate emulsion change in membrane stack material liquid tank is limpid, the calcium sulfate emulsion continuing to add brand-new proceeds membrane sepn;
4) when material concentration can not increase in membrane stack acid room or membrane stack alkali room, take out solution, by sulphuric acid concentration in sour room, by calcium hydroxide solid-liquid separation in alkali room, obtain sulfuric acid and calcium hydroxide product.
Described membrane stack material liquid tank is the film separating system that elementary cell is formed by two Bipolar Membrane, an anionic membrane and a cationic membrane.
The ionogen added in described room, pole refers to that electric conductivity value is the electrolyte solution of the Repone K of 10000-30000 μ S/cm, sodium-chlor or potassium sulfate.
Owing to have employed technique scheme, compared with prior art, the present invention levies current phosphogypsum application present situation, and adopting with phosphogypsum is raw material, pass through membrane separation process, industrial residue phosphogypsum is separated into sulfuric acid and calcium hydroxide, the disposable transformation efficiency of phosphogypsum reaches more than 72%, and in electrodialysis process, current efficiency reaches more than 65%, therefore, the method had both achieved the recycle of sulfuric acid in phosphorous chemical industry, again reduced production cost, for good basis is laid in the Sustainable development of phosphorous chemical industry.The present invention is simple, with low cost, and result of use is good.
Embodiment
Embodiments of the invention 1: membrane separation process utilizes phosphogypsum to prepare the method for sulfuric acid, get phosphogypsum 40g, and add suitable quantity of water, ball mill is adopted to be ground into slurry, then 800ml is diluted with water to, obtain the calcium sulfate emulsion that granularity is 1 μm, and calcium sulfate emulsion liquid is placed in the material room of membrane stack material liquid tank, taking 8g Repone K is dissolved in 800ml water, is added by this solution in room, pole, 1800ml water is added respectively in sour room and alkali room, be 25cm at area
2membrane stack in add volts DS 15V, open the recycle pump of each room, Bipolar Membrane is worked under electric field action, after 1.5 hours, calcium sulfate emulsion in membrane stack material liquid tank becomes limpid, continuing to increase mass concentration is that the new configuration calcium sulfate emulsion 20ml(of 50% is according to needs of production, if the volume of solution does not exceed the volume of membrane stack material liquid tank, then directly can add the calcium sulfate emulsion of brand-new, if add rear volume will exceed the volume of membrane stack material liquid tank, then need taking-up part to become limpid calcium sulfate emulsion), join in material room, after 0.5 hour, the sulphuric acid soln that concentration is 0.16mol/L is obtained respectively from sour room, muddy calcium hydroxide is obtained in alkali room, take out sulphuric acid soln in sour room and be concentrated into desired concn, by calcium hydroxide solid-liquid separation in alkali room, obtain High Purity Hydrogen calcium oxide product.
Embodiments of the invention 2: membrane separation process utilizes phosphogypsum to prepare the method for sulfuric acid, get phosphogypsum 40g, and add suitable quantity of water, ball mill is adopted to be ground into slurry, then 800ml is diluted with water to, obtain the calcium sulfate emulsion that granularity is 5 μm, and calcium sulfate emulsion liquid is placed in the material room of membrane stack material liquid tank; Taking 7g potassium sulfate is dissolved in 800ml water, and this solution is placed in room, pole; In acid and alkali room, add water 1500ml respectively, be 25cm at area
2membrane stack in add volts DS 15V, open the recycle pump of each room, Bipolar Membrane is worked under electric field action, after 1.5 hours, the solution in material room becomes limpid, continues to increase the new configuration calcium sulfate emulsion 30ml that mass concentration is 50%, join in material room, after 0.5 hour, from sour room, obtain the sulphuric acid soln that concentration is 0.2mol/L respectively, in alkali room, obtain muddy calcium hydroxide; Take out sulphuric acid soln in sour room and be concentrated into desired concn; By calcium hydroxide solid-liquid separation in alkali room, obtain High Purity Hydrogen calcium oxide product.
Claims (3)
1. membrane separation process utilizes phosphogypsum to prepare a method for sulfuric acid, it is characterized in that: comprise the steps:
1) phosphogypsum and water are ground pulping, be then diluted to that solid content is 4-20%, granularity is calcium sulfate emulsion between 0.3-10 μm, and calcium sulfate emulsion liquid is placed in membrane stack material liquid tank;
2) water is added to membrane stack acid room and membrane stack alkali room, in room, membrane stack pole, add sodium-chlor, Repone K or the potassium sulfate ionogen that mass concentration is 1%-20%, pass into direct supply respectively to room, two pole, control voltage is 5-50V, open the recycle pump of each room, Bipolar Membrane is worked under electric field action;
3) after 1-2h is carried out in reaction, after the calcium sulfate emulsion change in membrane stack material liquid tank is limpid, the calcium sulfate emulsion continuing to add brand-new proceeds membrane sepn;
4) when material concentration can not increase in membrane stack acid room or membrane stack alkali room, take out solution, by sulphuric acid concentration in sour room, by calcium hydroxide solid-liquid separation in alkali room, obtain sulfuric acid and calcium hydroxide product.
2. membrane separation process according to claim 1 utilizes phosphogypsum to prepare the method for sulfuric acid, it is characterized in that: described membrane stack material liquid tank is the film separating system that elementary cell is formed by two Bipolar Membrane, an anionic membrane and a cationic membrane.
3. membrane separation process according to claim 1 utilizes phosphogypsum to prepare the method for sulfuric acid, it is characterized in that: the ionogen added in described room, pole refers to that electric conductivity value is the electrolyte solution of the Repone K of 10000-30000 μ S/cm, sodium-chlor or potassium sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510019834.1A CN104591100A (en) | 2015-01-15 | 2015-01-15 | Method for preparing sulphuric acid from ardealite by membrane separation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510019834.1A CN104591100A (en) | 2015-01-15 | 2015-01-15 | Method for preparing sulphuric acid from ardealite by membrane separation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104591100A true CN104591100A (en) | 2015-05-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201510019834.1A Pending CN104591100A (en) | 2015-01-15 | 2015-01-15 | Method for preparing sulphuric acid from ardealite by membrane separation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105481273A (en) * | 2015-11-20 | 2016-04-13 | 天能水泥有限公司 | Method for utilizing collected dust from bypass of rotary kiln |
| CN106698497A (en) * | 2017-01-22 | 2017-05-24 | 武汉工程大学 | Method for preparing calcium sulfate from ardealite |
| CN113578916A (en) * | 2021-06-23 | 2021-11-02 | 常熟理工学院 | Method for realizing resource utilization of phosphogypsum by utilizing waste incineration fly ash |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5776328A (en) * | 1991-06-27 | 1998-07-07 | De Nora Permelec S.P.A. | Apparatus and process for electrochemically decomposing salt solutions to form the relevant base and acid |
| CN101481096A (en) * | 2009-02-19 | 2009-07-15 | 四川大学 | Technological process for producing sulphuric acid from waste gypsum and carbon dioxide and implementing membrane coupled reactor thereof |
| CN102899679A (en) * | 2012-10-24 | 2013-01-30 | 四川大学 | Method for coproducing sulfuric acid by utilizing gypsum mineralized CO2 |
-
2015
- 2015-01-15 CN CN201510019834.1A patent/CN104591100A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5776328A (en) * | 1991-06-27 | 1998-07-07 | De Nora Permelec S.P.A. | Apparatus and process for electrochemically decomposing salt solutions to form the relevant base and acid |
| CN101481096A (en) * | 2009-02-19 | 2009-07-15 | 四川大学 | Technological process for producing sulphuric acid from waste gypsum and carbon dioxide and implementing membrane coupled reactor thereof |
| CN102899679A (en) * | 2012-10-24 | 2013-01-30 | 四川大学 | Method for coproducing sulfuric acid by utilizing gypsum mineralized CO2 |
Non-Patent Citations (2)
| Title |
|---|
| 谢杰等: "液膜分离技术提取水中硫酸根的可行性分析", 《吉林建筑工程学院学报》 * |
| 顾莹莹等: "《废水是如何变清的 倾听地球的脉搏》", 30 April 2012, 冶金工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105481273A (en) * | 2015-11-20 | 2016-04-13 | 天能水泥有限公司 | Method for utilizing collected dust from bypass of rotary kiln |
| CN106698497A (en) * | 2017-01-22 | 2017-05-24 | 武汉工程大学 | Method for preparing calcium sulfate from ardealite |
| CN113578916A (en) * | 2021-06-23 | 2021-11-02 | 常熟理工学院 | Method for realizing resource utilization of phosphogypsum by utilizing waste incineration fly ash |
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Application publication date: 20150506 |
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