CN102633384A - Method for preparing phosphoric acid by recycling phosphorus from phosphorus-containing wastewater - Google Patents
Method for preparing phosphoric acid by recycling phosphorus from phosphorus-containing wastewater Download PDFInfo
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- CN102633384A CN102633384A CN2012101166857A CN201210116685A CN102633384A CN 102633384 A CN102633384 A CN 102633384A CN 2012101166857 A CN2012101166857 A CN 2012101166857A CN 201210116685 A CN201210116685 A CN 201210116685A CN 102633384 A CN102633384 A CN 102633384A
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Abstract
The invention discloses a method for preparing phosphoric acid by recycling phosphorus from phosphorus-containing wastewater. The method comprises the following steps: setting three stages of reactors and an intermediate equipment sedimentation tank, adding wastewater in the first-stage reactor, adding lime milk, and controlling the pH value, the reaction temperature and the reaction time of a liquid-phase mixture; after reaction, pumping into the sedimentation tank for sedimentation, filtering the underflow by a filtering system; adding the clear liquid of on the upper part of the sedimentation tank into a second-stage reactor, adding the lime milk at the same time and controlling the pH value, the reaction temperature and the reaction time of the liquid-phase mixture; after reaction, pumping into the sedimentation tank for sedimentation and recycling the upper-part clear liquid; introducing the solid after sedimentation into a three-stage reactor, adding sulfuric acid for treatment, and controlling the reaction temperature and the reaction time; filtering the obtained slurry, washing filter residue and stockpiling, then washing and recycling, wherein the filtrate is dilute phosphoric acid. The method disclosed by the invention ensures that phosphorus resource in the phosphorus-containing wastewater can be completely recycled, and is simple in process and operation, good in treatment effect, favorable in stability and low in cost.
Description
[technical field]
The present invention is relevant with water reuse, and is specifically, relevant with the utilization technology that produces waste water in the phosphorous chemical industry production process.
[background technology]
Phosphorous, the fluoric acid wastewater difficult treatment that produce during phosphorous chemical industry is produced.In the treating processes of high-density phosphorus, fluoric acid wastewater, adopt secondary lime acid-base neutralisation method at present more.And a large amount of sewage slag that will produce after the processing waste water, and the part addition material as phosphate fertilizer used after sewage slag can only adopt the slag dam heap to fill out or dry at present.The ZL200410009462.6 of Tsing-Hua University number " application of a kind of phosphorus-contained wastewater treating method and recovery phosphorus product thereof " is exactly to be flocculation agent with the molysite, and the quaternary ammonium salt Weibull is that coagulant aids is handled waste water, and the phosphorous throw out that obtains is as slow-release phosphate fertilizer.The applicant also once applied for " method of comprehensive utilization of wastewater of ammonium phosphate production " No. 201010267565.8; Disclose and passed through effluent segregation; Waste water according to the difference of ammonia-nitrogen content wherein, is mixed recycle in other production link respectively, realize the method for zero release; Also applied for No. 201110319541.7 " a kind of phosphorus-containing wastewater reclaim method ", effectively removed in the waste water in the phosphorus recovery of implementation part phosphorus.But aforesaid method is all failed a sewage slag and is thoroughly used, and the phosphor resource that is particularly contained in the slag fails thoroughly to reclaim, and still possibly cause the pollution of environment.Along with the raising of China to environmental protection requirement, in line with the principle that the filter resource is recycled as far as possible, for turning waste into wealth, the technician is still in the new processing scheme of exploitation simultaneously.
[summary of the invention]
The object of the present invention is to provide a kind of method of phosphorus-containing wastewater recovery phosphorus system phosphoric acid, to increase the approach that utilizes that produces waste water in the phosphorous chemical industry production process.
The contriver is through investigation and analysis, and the main composition of having grasped phosphorus-containing wastewater is following:
| Numbering | P 2O 5(％) | F(％) | As(％) | Pb(％) | Hg(％) | The pH value | Remarks |
| 1 | 3.58 | 0.72 | 0.0001 | 0.0002 | ﹤0.0001 | 1.29 | ? |
| 2 | 3.67 | 0.81 | 0.0001 | 0.0003 | ﹤0.0001 | 1.26 | ? |
| 3 | 3.37 | 1.29 | 0.0001 | 0.0004 | ﹤0.0001 | 1.18 | ? |
| 4 | 3.44 | 1.21 | 0.0001 | 0.0004 | ﹤0.0001 | 1.16 | ? |
| On average | 3.51 | 1.0075 | 0.0001 | 0.0003 | ﹤0.0001 | 1.22 | ? |
The contriver recognizes, fully reclaim the phosphorus in the waste water, needs to adopt it is carried out multiple-stage treatment, and therefore, the method that the contriver provides is that 3 stage reactors and intermediate equipment subsider thereof are set, and handles according to following steps then:
(1) in A reactor, add waste water, add the milk of lime for preparing simultaneously, the pH value of liquid phase mixture is controlled at 2～3, and temperature is controlled at 30 ℃～50 ℃, and the reaction times is 40～60 minutes; The yield of reaction back phosphorus is about 80%; Squeeze into subsider with pump after reaction finishes and carry out sedimentation, upper clear supernate gets into next stage and handles, and underflow goes filtering system;
(2) upper clear supernate after the sedimentation gets into the second order reaction groove, in the second order reaction groove, adds milk of lime simultaneously, and the pH value control of liquid phase mixture is in system 5～7, and temperature is controlled at 40 ℃～50 ℃, and the reaction times is about 30 minutes; The phosphorus yield of second order reaction is about 70%; Squeeze into subsider with pump after reaction finishes and carry out sedimentation, upper clear supernate is recycled; Solid after the sedimentation mainly is calcium phosphate salt, gets into next stage and handles;
(3) the phosphoric acid salt solid-phase material adding sulfuric acid that gets into three reactor carries out acidification, and temperature of reaction is controlled at 75 ℃～85 ℃, and the reaction times is 3～4 hours, obtains containing the phosphoric acid material pulp of calcium sulfate;
(4) phosphoric acid material pulp that contains calcium sulfate is through filtering, and filter residue washs with clear water, and the phosphogypsum after the washing is sent to and stored up, and wash water reclaims and is used for preparing lime milk; Filtered liq is a dilute phosphoric acid.
In the above-mentioned the first step, the massfraction of said milk of lime is controlled at 10%～15%.
In above-mentioned second step, the massfraction of said milk of lime is controlled at 15%～20%; It is to be used for the preparation of milk of lime or to be used for phosphoric acid production washing phosphogypsum that said upper clear supernate is recycled.
In above-mentioned the 3rd step, said vitriolic massfraction is 98.3%.
In above-mentioned the 4th step, conventional vacuum filtration is adopted in said filtration, the massfraction 25%～30% of said dilute phosphoric acid.
Use method of the present invention, can fully reclaim the phosphor resource in the phosphorus-containing wastewater, realize the recycle of waste water, have the following advantages: flow process and simple to operate, only need control pH value and temperature well, there is not other material adding; Treatment effect is good, good stability, and cost is low.
[description of drawings]
Fig. 1 is the FB(flow block) of the inventive method, in order to each step of explanation invention.
[
Embodiment]
Certain phosphate fertilizer plant of company uses present method, and 3 stage reactors and intermediate equipment subsider thereof are set.At first, in A reactor, add waste water, the massfraction that adding simultaneously prepares is 10% milk of lime, and the pH value of control liquid phase mixture is 2～3, and temperature is at 30 ℃～50 ℃, and the reaction times is 60 minutes; Squeeze into subsider with pump after reaction finishes and carry out sedimentation, underflow goes filtering system; Then the upper clear supernate with subsider gets into second reactor, adds massfraction simultaneously and be 15% milk of lime, and the pH value of control liquid phase mixture is 5～7, and 45 ℃ of temperature are about 30 minutes reaction times; Squeeze into subsider with pump after reaction finishes and carry out sedimentation, upper clear supernate reclaims; Solid after the sedimentation gets into three reactor, adds massfraction and is 98.3% sulfuric acid and handle, and temperature of reaction is controlled at 80 ℃, 3 hours reaction times; The slip that obtains is sent to behind the residue washing and is stored up through vacuum filtration, and wash water reclaims and is used for preparing lime milk; Filtered liq is dilute phosphoric acid.
Claims (5)
1. a phosphorus-containing wastewater reclaims the method for phosphorus system phosphoric acid, it is characterized in that this method is that 3 stage reactors and intermediate equipment subsider thereof are set, and handles according to following steps then:
(1) in A reactor, add waste water, add the milk of lime for preparing simultaneously, the pH value of liquid phase mixture is controlled at 2～3, and temperature is controlled at 30 ℃～50 ℃, and the reaction times is 40～60 minutes; The yield of reaction back phosphorus is about 80%; Squeeze into subsider with pump after reaction finishes and carry out sedimentation, upper clear supernate gets into next stage and handles, and underflow goes filtering system;
(2) upper clear supernate after the sedimentation gets into, and in the second order reaction groove, adds milk of lime simultaneously, and the pH value control of liquid phase mixture is in system 5～7, and temperature is controlled at 40 ℃～50 ℃, and the reaction times is about 30 minutes; The phosphorus yield of second order reaction is about 70%; Squeeze into subsider with pump after reaction finishes and carry out sedimentation, upper clear supernate is recycled; Solid after the sedimentation mainly is calcium phosphate salt, gets into next stage and handles;
(3) the phosphoric acid salt solid-phase material adding sulfuric acid that gets into three reactor carries out acidification, and temperature of reaction is controlled at 75 ℃～85 ℃, and the reaction times is 3～4 hours; Obtain containing the phosphoric acid material pulp of calcium sulfate;
(4) reaction back slip is through filtering, and filter residue washs with clear water, and the phosphogypsum after the washing is sent to and stored up, and wash water reclaims and is used for preparing lime milk; Filtered liq is a dilute phosphoric acid.
2. the method for claim 1 is characterized in that in the first step, and the massfraction of said milk of lime is controlled at 10%～15%.
3. the method for claim 1 is characterized in that the massfraction of said milk of lime is controlled at 15%～20% in second step; It is to be used for the preparation of milk of lime or to be used for phosphoric acid production washing phosphogypsum that said upper clear supernate is recycled.
4. the method for claim 1 is characterized in that said vitriolic massfraction is 98.3% in the 3rd step.
5. the method for claim 1 is characterized in that said filtration is conventional vacuum filtration in the 4th step, and the massfraction of said dilute phosphoric acid is 25%～30%.
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| CN2012101166857A CN102633384A (en) | 2012-04-20 | 2012-04-20 | Method for preparing phosphoric acid by recycling phosphorus from phosphorus-containing wastewater |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303884A (en) * | 2013-05-27 | 2013-09-18 | 瓮福（集团）有限责任公司 | Method for treating phosphorus concentrates and recovering phosphorus by using phosphogypsum slag dump pool water |
| CN103613181A (en) * | 2013-11-29 | 2014-03-05 | 瓮福（集团）有限责任公司 | Method for treating phosphogypsum slag dump pool water by using low-grade lime |
| CN103738931A (en) * | 2013-11-26 | 2014-04-23 | 瓮福（集团）有限责任公司 | Method for production of potassium dihydrogen phosphate from phosphorus-containing acidic wastewater |
| CN104401959A (en) * | 2014-10-13 | 2015-03-11 | 云南红富化肥有限公司 | Method for filtering phosphogypsum with dilute phosphoric acid for circulating washing |
| CN104803533A (en) * | 2015-04-14 | 2015-07-29 | 山东汇海医药化工有限公司 | Method for treating AABI (5-Acetoacetyl-amino-benzimidazolone) acylation wastewater |
| CN105884077A (en) * | 2016-04-13 | 2016-08-24 | 四川绵竹市盘龙矿物质有限责任公司 | Method for realizing total-closed wastewater circulation in feed-grade calcium hydrophosphate production process |
| CN106007051A (en) * | 2016-05-24 | 2016-10-12 | 瓮福（集团）有限责任公司 | Sewage treatment method for low-quality lime |
| CN106241851A (en) * | 2016-07-26 | 2016-12-21 | 四川高绿平环境科技有限公司 | A kind of processing method of useless phosphoric acid,diluted |
| CN107244688A (en) * | 2017-05-16 | 2017-10-13 | 同济大学 | A kind of method that phosphorous solid waste resource recovery is utilized |
| CN109761238A (en) * | 2019-03-22 | 2019-05-17 | 盛隆资源再生（无锡）有限公司 | A method of utilizing fluorine-containing phosphorous devil liquor recovery prodan and phosphoric acid |
| CN114249452A (en) * | 2020-09-25 | 2022-03-29 | 怀化恒一颜料化学有限公司 | Method for recovering phosphoric acid from quinacridone production wastewater |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303884A (en) * | 2013-05-27 | 2013-09-18 | 瓮福（集团）有限责任公司 | Method for treating phosphorus concentrates and recovering phosphorus by using phosphogypsum slag dump pool water |
| CN103738931A (en) * | 2013-11-26 | 2014-04-23 | 瓮福（集团）有限责任公司 | Method for production of potassium dihydrogen phosphate from phosphorus-containing acidic wastewater |
| CN103613181A (en) * | 2013-11-29 | 2014-03-05 | 瓮福（集团）有限责任公司 | Method for treating phosphogypsum slag dump pool water by using low-grade lime |
| CN104401959A (en) * | 2014-10-13 | 2015-03-11 | 云南红富化肥有限公司 | Method for filtering phosphogypsum with dilute phosphoric acid for circulating washing |
| CN104401959B (en) * | 2014-10-13 | 2016-06-22 | 云南红富化肥有限公司 | A kind of method filtering ardealite employing light phosphoric acid circulation washing |
| CN104803533A (en) * | 2015-04-14 | 2015-07-29 | 山东汇海医药化工有限公司 | Method for treating AABI (5-Acetoacetyl-amino-benzimidazolone) acylation wastewater |
| CN105884077A (en) * | 2016-04-13 | 2016-08-24 | 四川绵竹市盘龙矿物质有限责任公司 | Method for realizing total-closed wastewater circulation in feed-grade calcium hydrophosphate production process |
| CN106007051A (en) * | 2016-05-24 | 2016-10-12 | 瓮福（集团）有限责任公司 | Sewage treatment method for low-quality lime |
| CN106241851A (en) * | 2016-07-26 | 2016-12-21 | 四川高绿平环境科技有限公司 | A kind of processing method of useless phosphoric acid,diluted |
| CN106241851B (en) * | 2016-07-26 | 2018-01-05 | 四川高绿平环境科技有限公司 | A kind of processing method of useless phosphoric acid,diluted |
| CN107244688A (en) * | 2017-05-16 | 2017-10-13 | 同济大学 | A kind of method that phosphorous solid waste resource recovery is utilized |
| CN109761238A (en) * | 2019-03-22 | 2019-05-17 | 盛隆资源再生（无锡）有限公司 | A method of utilizing fluorine-containing phosphorous devil liquor recovery prodan and phosphoric acid |
| CN109761238B (en) * | 2019-03-22 | 2021-04-06 | 盛隆资源再生（无锡）有限公司 | Method for recovering sodium fluosilicate and phosphoric acid by using fluorine-containing and phosphorus-containing waste liquid |
| CN114249452A (en) * | 2020-09-25 | 2022-03-29 | 怀化恒一颜料化学有限公司 | Method for recovering phosphoric acid from quinacridone production wastewater |
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Application publication date: 20120815 |