CN103264998A - Recycle of calcium phosphate - Google Patents
Recycle of calcium phosphate Download PDFInfo
- Publication number
- CN103264998A CN103264998A CN2013101758657A CN201310175865A CN103264998A CN 103264998 A CN103264998 A CN 103264998A CN 2013101758657 A CN2013101758657 A CN 2013101758657A CN 201310175865 A CN201310175865 A CN 201310175865A CN 103264998 A CN103264998 A CN 103264998A
- Authority
- CN
- China
- Prior art keywords
- phosphorous acid
- waste residue
- sodium hypophosphite
- sodium
- technology
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to a process of extracting phosphorous acid from sodium hypophosphite slag, wherein a high purity phosphorous acid product is obtained specifically by a cation exchange method through decompression, distilling and crystallization. The process comprises the following steps: extracting calcium phosphate solid from a calcium phosphate in a calcium phosphate workshop and reacting with sodium carbonate; separating and purifying to obtain a sodium phosphite liquor; decompressing, evaporating and crystallizing the sodium phosphite liquor after cation exchange through D001 resin to obtain the high purity phosphorous acid product. The process is simple in process, less in energy consumption and high in product purity, and does not cause secondary pollution at the same time.
Description
Technical field
The present invention relates to a kind of technology of from the sodium hypophosphite waste residue, extracting phosphorous acid, specifically adopt base exchange method, obtain highly purified phosphorous acid finished product through the underpressure distillation crystallization.
Background technology
The demand of sodium hypophosphite is along with chemical nickel plating range of application and production-scale continuous expansion and increase.China is sodium hypophosphite big producing country, industrialized preparing process generally adopts single stage method both at home and abroad at present, also produced the lime precipitation that contains a large amount of phosphorous acid calcium when this technology obtains sodium hypophosphite, this by product is used for filling out the hole as waste residue usually, has polluted environment.
The treatment process of waste residue in the disclosed sodium hypophosphite production course among the patent documentation CN101172593: waste residue is put into stove, carry out the flame calcining with Sweet natural gas or diesel oil, send into oxygen simultaneously, calcining temperature control becomes phosphorus to generate the calcium phosphate product phosphorus oxidation in the waste residue calcium phosphite under 1100 ~ 1200 ℃.
Above-mentioned technological operation flow process complexity, processing condition are had relatively high expectations, and energy consumption is also high simultaneously.
Summary of the invention
The objective of the invention is from the sodium hypophosphite waste residue, to extract the technology of phosphorous acid.
To achieve these goals, the present invention will extract phosphorous acid calcium solid and soda ash reaction from the plate-and-frame filter press of sodium hypophosphite production plant after, separate out and purifying obtain sodium phosphite solution, sodium phosphite solution carries out cationic exchange through the D001 resin and obtains highly purified phosphorous acid finished product by the reduction vaporization crystallization.
Specifically be that technology comprises: 1) the waste residue input with sodium hypophosphite has in the reactor of agitator, adds water and stirs, and feed the steam intensification, simultaneously the slow soda ash that adds; 2) above-mentioned feed liquid is squeezed in the plate-and-frame filter press with fresh feed pump, remove precipitation of calcium carbonate after, filtrate is dropped into filtrate receiver; 3) with filtrate by in and pump squeeze in and still, in it and still add pre-configured phosphorous acid, add the H that generating unit produces
2S removes heavy metal through plate-and-frame filter press, passes through film filter again, obtains sodium phosphite solution at last, wherein H
2S is by utilizing the generation of sodium sulphite and phosphatase reaction in the hydrogen sulfide reactor, excessive H in the while filtrate
2S recycles through aeration tower; 4) above-mentioned sodium phosphite solution feeding is equipped with on the cationic exchange coloum of D001 resin, carries out cationic exchange; 5) filtrate obtains high-purity phosphorous acid finished product through the underpressure distillation crystallization behind the centrifuge dewatering.
Advantage of the present invention: the phosphorous acid that adopts technology of the present invention to obtain has simple, the less energy consumption of technology, and the product purity height does not bring secondary pollution simultaneously.
Description of drawings
Fig. 1 extracts the process flow sheet of phosphorous acid from the sodium hypophosphite waste residue
In the accompanying drawing 1, reactor, 2, fresh feed pump, 3, plate-and-frame filter press, 4, filtrate receiver, 5, in and pump, 6, in and still, 7, the hydrogen sulfide reactor, 8, cation exchange tower, 9, plate-and-frame filter press, 10, depriving hydrogen sulphide aeration tower, 11, film filter, 12, crystallization kettle, 13, whizzer.
Specific embodiment
Embodiment 1:
From the plate-and-frame filter press of sodium hypophosphite production plant, get the solid precipitation 400g that contains 48% phosphorous acid calcium, put into the 2L flask that has stirring behind the water flush away sodium hypophosphite wherein, add water 1000ml, after the heated and stirred, add soda ash 180g, feed liquid is warmed up to 85 ℃, insulated and stirred reaction 10h, elimination precipitation of calcium carbonate while hot.Add the recovery phosphorous acid solution 47g that contains 50% phosphorous acid of preparation in advance, regulate pH to 5 ~ 6, remove excessive soda ash, feed H
2After S removes heavy metal, obtain 13.6% sodium phosphite solution 1530g, wherein H
2S is by utilizing the generation of sodium sulphite and phosphatase reaction in the hydrogen sulfide reactor, excessive H in the while filtrate
2S recycles through aeration tower.
On the cationic exchange coloum that the D001 resin is housed, the sodium phosphite solution that obtains is carried out cationic exchange with the speed of 20ml/min, obtain containing the phosphorous acid solution 1355g of phosphorous acid 9.5%.Through 80 ℃, vacuum tightness is underpressure distillation 1 hour under the 0.05-0.07MPa, obtains the phosphorous acid crystal product 131g of content 99.8% after the centrifuge dehydration.
Embodiment 2:
From the plate-and-frame filter press of sodium hypophosphite production plant, get the solid precipitation 400g that contains 50% phosphorous acid calcium, put into the 2L flask that stirring is housed behind the water flush away sodium hypophosphite wherein, add water 1000ml, after the heated and stirred, add soda ash 185g, feed liquid is warmed up to 90 ℃, insulated and stirred reaction 10h, elimination precipitation of calcium carbonate while hot.Add the recovery phosphorous acid liquid 47g that contains 50% phosphorous acid of preparation in advance, regulate pH to 5 ~ 6, remove excessive soda ash, feed H
2After S removes heavy metal, obtain 14% sodium phosphite solution 1535g, wherein H
2S is by utilizing the generation of sodium sulphite and phosphatase reaction in the hydrogen sulfide reactor, excessive H in the while filtrate
2S recycles through aeration tower.
On the cationic exchange coloum that the D001 resin is housed, the sodium phosphite solution that obtains is carried out cationic exchange with the speed of 15ml/min, obtain containing the phosphorous acid solution 1470g of phosphorous acid 10.68%.Through 80 ℃, vacuum tightness is underpressure distillation 1 hour under the 0.05-0.07MPa, obtains the phosphorous acid crystal product 148g of content 99.5% after the centrifuge dehydration.
Embodiment 3:
From the plate-and-frame filter press of sodium hypophosphite production plant, get the solid precipitation 400g that contains 52% phosphorous acid calcium, put into the 2L flask that stirring is housed behind the water flush away sodium hypophosphite wherein, add water 1000ml, after the heated and stirred, add soda ash 180g, feed liquid is warmed up to 85 ℃, insulated and stirred reaction 5h, elimination precipitation of calcium carbonate while hot.Add the recovery phosphorous acid liquid 47g that contains 50% phosphorous acid of preparation in advance, regulate pH to 5 ~ 6, remove excessive soda ash, feed H
2After S removes heavy metal, obtain 13.8% sodium phosphite solution 1550g, wherein H
2S is by utilizing the generation of sodium sulphite and phosphatase reaction in the hydrogen sulfide reactor, excessive H in the while filtrate
2S recycles through aeration tower.
On the cationic exchange coloum that the D001 resin is housed, the sodium phosphite solution that obtains is carried out cationic exchange with the speed of 20ml/min, obtain containing the phosphorous acid solution 1450g of phosphorous acid 9.5%.Through 80 ℃, vacuum tightness is underpressure distillation 1 hour under the 0.05-0.07MPa, obtains the phosphorous acid crystal product 145g of content 99.9% after the centrifuge dehydration.
Claims (8)
1. technology of extracting phosphorous acid from the sodium hypophosphite waste residue is characterized in that comprising following processing step:
1) the sodium hypophosphite waste residue that will contain phosphorous acid calcium after the plate-and-frame filter press press filtration drops into and to have in the jacket reactor of agitator, adds water and stirs, and jacket reactor is fed steam heat up, and slowly adds soda ash simultaneously;
2) above-mentioned feed liquid is squeezed in the plate-and-frame filter press with fresh feed pump, remove precipitation of calcium carbonate after, filtrate is dropped into filtrate receiver;
3) with filtrate by in and pump squeeze in and still, wherein in and still add pre-configured phosphorous acid, remove excessive soda ash;
4) above-mentioned sodium phosphite solution feeding is equipped with on the cation exchange tower of D001 large hole cation exchanger resin, carries out cationic exchange;
5) filtrate of carrying out after the cationic exchange feeds H
2S once removes by filter heavy metal through plate-and-frame filter press;
6) the sodium phosphite solution after the press filtration is removed excessive hydrogen sulfide through the depriving hydrogen sulphide aeration tower, hydrogen sulfide is recycled to hydrogen sulfide generator, and filtrate is carried out secondary filtration through film filter again, obtains the phosphorous acid solution made from extra care at last;
7) with the phosphorous acid filtrate of exquisiteness at 80 ℃, vacuum tightness be under the 0.05-0.07MPa through underpressure distillation 1 hour, obtain high-purity phosphorous acid crystal product behind the centrifuge dewatering.
2. a kind of technology of extracting phosphorous acid from the sodium hypophosphite waste residue according to claim 1 is characterized in that, contains 45 ~ 55% phosphorous acid calcium in the filter residue at least.
3. a kind of technology of extracting phosphorous acid from the sodium hypophosphite waste residue according to claim 1 is characterized in that, the waste residue of sodium hypophosphite in the step 1), and water, the mass ratio that feeds intake of soda ash is 1.8-2.4:4-6:0.8-1.5.
4. a kind of technology of extracting phosphorous acid from the sodium hypophosphite waste residue according to claim 1 is characterized in that, feed liquid feeds steam and is warming up to 80-85 ℃ in the step 1), simultaneously insulated and stirred 5-8h.
5. a kind of technology of extracting phosphorous acid from the sodium hypophosphite waste residue according to claim 1 is characterized in that, the input mass concentration is 50% phosphorous acid solution 40-50g in the step 3), and regulates pH to 5-6.
6. a kind of technology of from the sodium hypophosphite waste residue, extracting phosphorous acid according to claim 1, it is characterized in that, step 4) Central Asia sodium radio-phosphate,P-32 solution is carried out cationic exchange with the speed of 20mL/min in the cation exchange tower of D001 large hole cation exchanger resin.
7. a kind of technology of extracting phosphorous acid from the sodium hypophosphite waste residue according to claim 1 is characterized in that H
2S is by utilizing the generation of sodium sulphite and phosphatase reaction in the hydrogen sulfide reactor, excessive H in the while filtrate
2S recycles through aeration tower.
8. a kind of technology of extracting phosphorous acid from the sodium hypophosphite waste residue according to claim 1 is characterized in that the phosphorous acid content that obtains is higher than 99.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101758657A CN103264998A (en) | 2013-05-14 | 2013-05-14 | Recycle of calcium phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101758657A CN103264998A (en) | 2013-05-14 | 2013-05-14 | Recycle of calcium phosphate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103264998A true CN103264998A (en) | 2013-08-28 |
Family
ID=49008678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013101758657A Pending CN103264998A (en) | 2013-05-14 | 2013-05-14 | Recycle of calcium phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103264998A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104876201A (en) * | 2014-02-28 | 2015-09-02 | 湖北尧治河化工股份有限公司 | Circulating clean production technology for combined production of sodium hypophosphite, sodium phosphite and calcium hydroxide |
| CN106395773A (en) * | 2016-08-31 | 2017-02-15 | 无锡中天固废处置有限公司 | Method for recovering phosphorous acid out of spent electroless nickel-plating bath |
| CN106925100A (en) * | 2015-12-29 | 2017-07-07 | 天津市英派克石化工程有限公司 | A kind of phosphinic acids sodium produces the method that waste residue prepares desulfurizing agent |
| CN107029642A (en) * | 2017-05-08 | 2017-08-11 | 宜兴市宏博精细化工有限公司 | A kind of oxyquinoline preparation facilities of 5 chlorine 8 |
| CN110451469A (en) * | 2019-08-21 | 2019-11-15 | 武汉工程大学 | A kind of processing method of Sodium hypophosphite production residue |
| CN110902664A (en) * | 2019-12-11 | 2020-03-24 | 无锡市张舍化工有限公司 | Method for reducing chloride ions in phosphorous acid |
| CN111847413A (en) * | 2020-06-23 | 2020-10-30 | 惠州Tcl环境科技有限公司 | Method for preparing trisodium phosphate by using phosphoric acid-containing waste material |
| CN112010275A (en) * | 2020-08-31 | 2020-12-01 | 江苏康祥实业集团有限公司 | Recycling process for sodium hypophosphite production residues |
| CN114014286A (en) * | 2021-11-14 | 2022-02-08 | 云南福石科技有限公司 | Method for producing potassium phosphite by using sodium hypophosphite slag |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4380531A (en) * | 1981-10-21 | 1983-04-19 | Occidental Chemical Corporation | Process for preparing phosphorus acid from industrial waste materials |
| CN101172593A (en) * | 2007-10-08 | 2008-05-07 | 江苏康祥集团公司 | Method of processing waste slag in sodium hypophosphite production process |
| CN103011454A (en) * | 2012-12-10 | 2013-04-03 | 中国地质大学（武汉） | Terrestrial heat tail water treating process |
-
2013
- 2013-05-14 CN CN2013101758657A patent/CN103264998A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4380531A (en) * | 1981-10-21 | 1983-04-19 | Occidental Chemical Corporation | Process for preparing phosphorus acid from industrial waste materials |
| CN101172593A (en) * | 2007-10-08 | 2008-05-07 | 江苏康祥集团公司 | Method of processing waste slag in sodium hypophosphite production process |
| CN103011454A (en) * | 2012-12-10 | 2013-04-03 | 中国地质大学（武汉） | Terrestrial heat tail water treating process |
Non-Patent Citations (1)
| Title |
|---|
| 王惠平等: "从次磷酸钠生产废渣中提取亚磷酸", 《江苏化工》, 31 August 1998 (1998-08-31) * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104876201A (en) * | 2014-02-28 | 2015-09-02 | 湖北尧治河化工股份有限公司 | Circulating clean production technology for combined production of sodium hypophosphite, sodium phosphite and calcium hydroxide |
| CN104876201B (en) * | 2014-02-28 | 2017-07-07 | 湖北尧治河化工股份有限公司 | A kind of process for cleanly preparing of coproduction sodium hypophosphite, sodium phosphite and calcium hydroxide recycled |
| CN106925100A (en) * | 2015-12-29 | 2017-07-07 | 天津市英派克石化工程有限公司 | A kind of phosphinic acids sodium produces the method that waste residue prepares desulfurizing agent |
| CN106395773A (en) * | 2016-08-31 | 2017-02-15 | 无锡中天固废处置有限公司 | Method for recovering phosphorous acid out of spent electroless nickel-plating bath |
| CN107029642A (en) * | 2017-05-08 | 2017-08-11 | 宜兴市宏博精细化工有限公司 | A kind of oxyquinoline preparation facilities of 5 chlorine 8 |
| CN110451469A (en) * | 2019-08-21 | 2019-11-15 | 武汉工程大学 | A kind of processing method of Sodium hypophosphite production residue |
| CN110902664A (en) * | 2019-12-11 | 2020-03-24 | 无锡市张舍化工有限公司 | Method for reducing chloride ions in phosphorous acid |
| CN111847413A (en) * | 2020-06-23 | 2020-10-30 | 惠州Tcl环境科技有限公司 | Method for preparing trisodium phosphate by using phosphoric acid-containing waste material |
| CN112010275A (en) * | 2020-08-31 | 2020-12-01 | 江苏康祥实业集团有限公司 | Recycling process for sodium hypophosphite production residues |
| CN114014286A (en) * | 2021-11-14 | 2022-02-08 | 云南福石科技有限公司 | Method for producing potassium phosphite by using sodium hypophosphite slag |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103264998A (en) | Recycle of calcium phosphate | |
| CN100558633C (en) | The method for preparing PHOSPHORIC ACID TECH.GRADE, food grade phosphoric acid and industrial monoammonium phosphate with phosphoric acid by wet process | |
| JP6931284B2 (en) | How to make taurine | |
| JP2015501331A (en) | Method for producing taurine | |
| CN111086977B (en) | Method for preparing MCP and MDCP (Madin-Darby Canine phosphate) by using raffinate acid | |
| CN101348299A (en) | Glyphosate synthesized mother liquor processing method | |
| CN103303886A (en) | Novel method for producing industrial phosphoric acid by purification with wet process phosphoric acid | |
| CN102320585A (en) | Method for direct production of industrial-grade ammonium biphosphate by wet-process phosphoric acid | |
| CN101182281A (en) | Method for refining biodiesel byproduct glycerin | |
| CN202038998U (en) | Production system for recycling carbolic oil through acidolysis separation of phenol sodium salt and co-producing sodium sulfite | |
| CN114988380A (en) | Method for producing food-grade monopotassium phosphate and co-producing high-purity gypsum by using feed-grade calcium hydrophosphate | |
| CN103213962A (en) | Method for preparing feed-grade calcium hydrophosphate from phosphoric acid-containing mixed acid etching waste liquid | |
| CN108569812B (en) | Treatment system and treatment method for wastewater containing low-concentration sulfuric acid | |
| CN104086439A (en) | Method for recovering pregabalin intermediate resolving agent (R)-(+)-alpha-phenylethylamine | |
| CN104387255B (en) | Preparation method of calcium formate | |
| CN101747301B (en) | Method for preparing vitamin C with low consumption | |
| CN102875401B (en) | Method for producing DL-aspartic acid from waste radix asparagi | |
| CN105293796A (en) | Method for co-production of sodalumite and gypsum through activated clay production mother liquid | |
| CN101857212A (en) | Method for preparing food-grade monoammonium phosphate from wet-process phosphoric acid | |
| CN103303883B (en) | A kind of production technique of phosphorus oxychloride | |
| CN102925294A (en) | Mehtod for preparing biodiesel by floating slag from in-situ esterification sewage treatment plant | |
| CN105271153A (en) | Method for preparing potassium dihydrogen phosphate from wet phosphoric acid | |
| CN205634920U (en) | Utilize device of acid etching solution and alkaline etching liquid preparation oxo -chlorination copper | |
| CN206143108U (en) | Retrieve polyether glycol and potassium dihydrogen phosphate's device in follow polyether glycol filter residue | |
| CN112047401B (en) | Method for thickening and refining seawater by using sodium sulfate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130828 |