CN101774557A - Method for producing phosphoric acid with titanium white waste - Google Patents
Method for producing phosphoric acid with titanium white waste Download PDFInfo
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- CN101774557A CN101774557A CN201010113473A CN201010113473A CN101774557A CN 101774557 A CN101774557 A CN 101774557A CN 201010113473 A CN201010113473 A CN 201010113473A CN 201010113473 A CN201010113473 A CN 201010113473A CN 101774557 A CN101774557 A CN 101774557A
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Abstract
The invention provides a method for producing phosphoric acid with titanium white waste, which is an improvement and innovation based on ZL03125193.5. The invention adopts the acid mixing process twice, and combines the requirements of the phosphoric acid by wet process for the acid concentration and the acid temperature, thereby completely satisfying the needs of industrial production and producing good economic benefits and social benefits.
Description
Technical field
The present invention relates to a kind of integrated conduct method of titanium white waste acid, specifically a kind of titanium white waste acid is used to produce the method for phosphoric acid by wet process.
Background technology
The industrial production of titanium dioxide has sulfuric acid process and two kinds of processing methodes of chlorination process.Sulfuric acid process is with a long history, and technical maturity is strong to titanium material adaptability, and can produce anatase titanium dioxide and two kinds of products of rutile-type, but also has long flow path, energy consumption height, the shortcoming that three wastes discharge amount is big, wherein spent acid especially.Adopting Titanium White Production By Sulfuric Acid Process, 1 ton of titanium dioxide of every production approximately to produce concentration is spent acid 6～8t of about 20%.So many spent acid returns the dilution water that is used for the titanium dioxide hydrolysis procedure and leaches the water except about 20%, and how all the other spent acid of 80% of digestion process are keys of sulfate process titanium dioxide Business survival and development.Present both economical way, be exactly that titanium white waste acid is concentrated, impurity crystallizations from spent acid such as ferrous sulfate are separated out, thereby reduce the iron level in the spent acid greatly, be implemented in to recycle or fully utilize in the titanium white device and be used for producing general calcium, phosphoric acid, industrial sulphuric acid salt etc.Spent acid concentrates the general method that adopts submerged combustion and vacuum concentration, submerged combustion is directly to spray into the high-temperature gas that produces in the combustion chamber in the spent acid, make the moisture evaporation in the spent acid and play the effect of concentrating waste acid, because the raising of sulfuric acid concentration is separated out the ferrous sulfate that is dissolved in the spent acid.But the concentration after this method concentrates is not high, and equipment corrosion is very serious.CN1376635 discloses a kind of production method that is used to produce phosphoric acid by wet process with the by-product sulfuric acid of Titanium White Production By Sulfuric Acid Process, it at first carries out dilute sulphuric acid and elevated temperature heat gas counter current contact flash evapn and concentrates, the impurity compound that contains in diluted acid precipitates with the rising of temperature and acid concentration separates out, behind the crystallisation by cooling separating impurity and the vitriol oil be made into finite concentration and be used further to produce phosphoric acid by wet process.The crucial part of this method is that also spent acid concentrates, and it is not only invested greatly, the working cost height, and also very strict to the requirement of equipment material, be difficult to satisfy need of industrial production.Vacuum-evaporation concentrates can be according to its evaporation capacity, concentrate progression, respectively about 20% spent acid is concentrated into more than 40%, 50%, 70% even 90%.Germany Bayer AG adopts this method, in multiple-effect falling film vaporizer and pump circulation thickener, with steam is that the thermal source segmentation is concentrated to 70～80% with spent acid, but the ferrous sulfate monohydrate that the dehydration of two sections concentrated iron vitriols later on generates seriously stops up the tubulation of vaporizer.So this method also be difficult to realize the continous-stable operation of spent acid concentrating unit, general safely can only carry densely to 30～40%, and plant investment is big, technical process complexity, working cost height.ZL03125193.5 provides a kind of method of producing general calcium with titanium white waste acid, it is well in conjunction with general calcium working condition, adopt secondary complex acid technology, avoided spent acid to concentrate a series of difficult problems of bringing, solved the influence that the sulfate industry iron in the spent acid is produced general calcium well, have reduced investment, easy and simple to handle, the advantage that working cost is low.But specific to the production of phosphoric acid by wet process, because its requirement difference dense to reaction acid and sour temperature, so operational path will improve, technic index needs further to adjust.
Summary of the invention
The present invention is improvement on the ZL03125193.5 basis and innovation just, combines the requirement of Wet-process Phosphoric Acid Production to sour concentrated acid temperature, and the method that provides a kind of titanium white waste acid to be used for Wet-process Phosphoric Acid Production can satisfy need of industrial production fully.
The concrete technical scheme that realizes the object of the invention is: titanium white waste acid be mixed with quadratic acid with the vitriol oil in proportion through the preparating acid that complex acid obtains, enter thickener, this moment, the solid sulphuric acid of separating out ferrously entered whizzer or pressure filter carries out liquid-solid separation after thickening, filter cake is the raw materials for production of solid sulphuric acid industry iron as iron oxide black, filtrate is returned thickener, the more clear acid solution that disappears enters the diluted acid storage tank through the thickener overflow port, send into the complex acid device again and be mixed into preparating acid one time with the vitriol oil, after removing heat by graphite heat exchanger, a part is made into the secondary preparating acid with titanium white waste acid again, and another part is sent to Wet-process Phosphoric Acid Production and uses.Specifically may further comprise the steps:
(1), preparating acid of part that titanium white waste acid and the vitriol oil are obtained through complex acid secondary complex acid by a certain percentage;
(2), in thickener, carry out the secondary preparating acid that obtains settlement separate;
(3), thickener underflow slag acid removes solid settlement things such as ferrous sulfate through solid-liquid separating equipment, the purification acid that obtains continues to return thickener;
(4), clarifying secondary preparation acid solution enters the diluted acid storage tank through the thickener overflow port, carries out complex acid by a certain percentage one time with the vitriol oil again;
Preparating acid of the part that (5), will obtain is sent to Wet-process Phosphoric Acid Production and uses.
Wherein, the described titanium white waste acid of step (1) has preferably passed through pre-concentration, because can reduce fresh vitriol oil consumption; After particularly passing through titanium dioxide calcining kiln kiln tail waste heat pre-concentration, acid-spending strength can reach about 30%, and fresh vitriol oil consumption can reduce more than one times, and economy of the present invention and suitability are more outstanding.
The described secondary preparating acid acid of step (2) is dense preferably to be controlled at 65～70%, because bring up at 64% o'clock at 55 ℃ of sulfuric acid concentrations, the solubleness of sulfate industry iron only 0.6%, at this time the content of ferrous sulfate has been not enough to the production of phosphoric acid by wet process is exerted an influence in the spent acid.In addition, for improving the effect of thickener, can add an amount of flocculation agents such as polyacrylamide and help sedimentation.
The described solid-liquid separating equipment of step (3) is whizzer or pressure filter.
The described preparating acid acid of step (5) is dense to be controlled at 80～90%, best 85～90%, and this is based on, and Wet-process Phosphoric Acid Production is dense to acid, the requirement of acid temperature, has taken into account the smooth and easy of complex acid technical process simultaneously.
Accompanying drawing is a process flow sheet of the present invention.
Below in conjunction with accompanying drawing the present invention is described in detail:
Titanium white waste acid with in complex acid device 1, be mixed with quadratic acid in proportion from a preparating acid of a preparating acid storage tank 6, enter thickener 2, the ferrous grade of the solid sulphuric acid of separating out this moment solid impurity enters whizzer after the thickening sedimentation or pressure filter 3 carries out liquid-solid separation, filter cake is the ferrous solid impurity that waits of solid sulphuric acid, filtrate is returned thickener 2, more clarifying acid solution enters secondary preparating acid storage tank 4 through thickener 2 overflow ports, send into complex acid device 5 again and be mixed into preparating acid one time with the vitriol oil, send into preparating acid storage tank 6 one time after removing heat by graphite heat exchanger, preparating acid recirculation of a part and titanium white waste acid are made into the secondary preparating acid, and another part is sent to Wet-process Phosphoric Acid Production and uses.
Claims (7)
1. method that titanium white waste acid is used to produce phosphoric acid comprises following concrete steps:
(1), preparating acid of part that titanium white waste acid and the vitriol oil are obtained through complex acid secondary complex acid by a certain percentage;
(2), in thickener, carry out the secondary preparating acid that obtains settlement separate;
(3), thickener underflow slag acid removes solid settlement things such as ferrous sulfate through solid-liquid separating equipment, the purification acid that obtains continues to return thickener;
(4), clarifying secondary preparation acid solution enters the diluted acid storage tank through the thickener overflow port, carries out complex acid by a certain percentage one time with the vitriol oil again;
Preparating acid of the part that (5), will obtain is sent to Wet-process Phosphoric Acid Production and uses.
2. described method of claim 1, wherein the described titanium white waste acid of step (1) is through pre-concentration.
3. described method of claim 2, wherein the described titanium white waste acid of step (1) through titanium dioxide calcining kiln kiln tail waste heat pre-concentration to 30% about.
4. claim 1 or 3 described methods, wherein the described secondary preparating acid acid of step (2) is dense preferably is controlled at 65～70%.
5. described method of claim 4, wherein the described solid-liquid separating equipment of step (3) is whizzer or pressure filter.
6. described method of claim 4, wherein the described preparating acid acid of step (5) is dense is controlled at 80～90%.
7. described method of claim 6, wherein the described preparating acid acid of step (5) is dense is controlled at 85～90%.
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| CN201010113473A CN101774557A (en) | 2010-02-21 | 2010-02-21 | Method for producing phosphoric acid with titanium white waste |
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| CN201010113473A CN101774557A (en) | 2010-02-21 | 2010-02-21 | Method for producing phosphoric acid with titanium white waste |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502546A (en) * | 2011-11-28 | 2012-06-20 | 安徽六国化工股份有限公司 | Titanium white waste acid utilization method |
| WO2013174061A1 (en) * | 2012-05-25 | 2013-11-28 | 四川龙蟒磷化工有限公司 | Method for preparing high quality feed grade calcium hydrogen phosphate using by-product waste acid from titanium dioxide production |
| WO2013174062A1 (en) * | 2012-05-25 | 2013-11-28 | 四川龙蟒钛业股份有限公司 | Method for pre-treating phosphorus rock by mixture of titanium dioxide waste acid and fluorine-containing waste water |
| CN103420350A (en) * | 2013-09-04 | 2013-12-04 | 安徽新中远化工科技有限公司 | Method for removing impurities in phosphoric acid |
| CN104140082A (en) * | 2014-07-31 | 2014-11-12 | 四川龙蟒钛业股份有限公司 | Method for recycling titanium dioxide waste acid |
| CN104874590A (en) * | 2014-02-27 | 2015-09-02 | 龚家竹 | Resource processing method of chlorination waste residue |
| CN106315521A (en) * | 2016-08-18 | 2017-01-11 | 四川龙蟒钛业股份有限公司 | Recycling method of titanium dioxide waste acid |
| CN113292055A (en) * | 2021-06-25 | 2021-08-24 | 甘肃东方钛业有限公司 | Method for producing phosphoric acid by recycling waste sulfuric acid and acid wastewater generated in titanium dioxide production process |
-
2010
- 2010-02-21 CN CN201010113473A patent/CN101774557A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502546A (en) * | 2011-11-28 | 2012-06-20 | 安徽六国化工股份有限公司 | Titanium white waste acid utilization method |
| CN102502546B (en) * | 2011-11-28 | 2013-10-23 | 安徽六国化工股份有限公司 | Titanium white waste acid utilization method |
| WO2013174061A1 (en) * | 2012-05-25 | 2013-11-28 | 四川龙蟒磷化工有限公司 | Method for preparing high quality feed grade calcium hydrogen phosphate using by-product waste acid from titanium dioxide production |
| WO2013174062A1 (en) * | 2012-05-25 | 2013-11-28 | 四川龙蟒钛业股份有限公司 | Method for pre-treating phosphorus rock by mixture of titanium dioxide waste acid and fluorine-containing waste water |
| CN103420350A (en) * | 2013-09-04 | 2013-12-04 | 安徽新中远化工科技有限公司 | Method for removing impurities in phosphoric acid |
| CN103420350B (en) * | 2013-09-04 | 2016-03-02 | 安徽新中远化工科技有限公司 | The minimizing technology of impurity in a kind of phosphoric acid |
| CN104874590A (en) * | 2014-02-27 | 2015-09-02 | 龚家竹 | Resource processing method of chlorination waste residue |
| CN104140082A (en) * | 2014-07-31 | 2014-11-12 | 四川龙蟒钛业股份有限公司 | Method for recycling titanium dioxide waste acid |
| CN104140082B (en) * | 2014-07-31 | 2016-08-24 | 四川龙蟒钛业股份有限公司 | A kind of recoverying and utilizing method of titanium white waste acid |
| CN106315521A (en) * | 2016-08-18 | 2017-01-11 | 四川龙蟒钛业股份有限公司 | Recycling method of titanium dioxide waste acid |
| CN113292055A (en) * | 2021-06-25 | 2021-08-24 | 甘肃东方钛业有限公司 | Method for producing phosphoric acid by recycling waste sulfuric acid and acid wastewater generated in titanium dioxide production process |
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Open date: 20100714 |