CN85100438B - Process for recovering potssium form k2sif6-bearing gypsum - Google Patents
Process for recovering potssium form k2sif6-bearing gypsum Download PDFInfo
- Publication number
- CN85100438B CN85100438B CN85100438A CN85100438A CN85100438B CN 85100438 B CN85100438 B CN 85100438B CN 85100438 A CN85100438 A CN 85100438A CN 85100438 A CN85100438 A CN 85100438A CN 85100438 B CN85100438 B CN 85100438B
- Authority
- CN
- China
- Prior art keywords
- gypsum
- potassium
- acid
- jie
- sour
- 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.)
- Expired
Links
Classifications
-
- 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
- C01F11/46—Sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to a method for recovering kalium in gypsum containing potassium fluosilicate, which has the technical scheme that calcium oxide in a neutral or alkaline solution is repulped, and insoluble potassium fluorosilicate in gypsum is acidized, the potassium fluorosilicate in the acidized gypsum is decomposed, and the potassium fluorosilicate and dihydrate gypsum react to produce a potassium sulfate solution; the repulped mother solution (potassium sulfate) can be used as a cleaning solution of the acidized gypsum which is solidified in an acidizing system. The present invention has the advantages of simple operation complete reaction, and low price and easy acquisition of auxiliary materials; 90 to 95 wt % of potassium in the acidized gypsum can be recovered, the sulfuric acid consumption for acidizing reaction is reduced, and residual acid pollution in the acidized gypsum can be simultaneously eliminated by the calcium oxide.
Description
The present invention generates potassium recovery technology in the fluorine-containing silicic acid syngenite when belonging to phosphorus ore direct method potassium dihydrogen phosphate making or potassium-ammonium phosphate.
In prior art, utilize sal enixum or vitriolate of tartar, sulfuric acid, the flow process of acid Jie's phosphorus ore direct production potassium primary phosphate or potassium-ammonium phosphate has been acknowledged as a both economical method of producing high-efficiency compound fertilizer, but because a large amount of potassium ions is introduced in acid Jie process, make with phosphorus ore in divide the fluorine be situated between out and silicon dioxde reaction to generate the very little potassium silicofluoride of molten Jie's degree to follow and be sunken in the gypsum, though this method can stop the effusion of fluorine when phosphorus ore acid is situated between reaction, basically eliminated the topsoil of fluorine in the phosphatic manure, obtain the acid solution of low fluorine, but a large amount of potassium has been depleted, the loss of general potassium accounts for 15～25%(weight that this production method is always thrown the potassium amount), if that these are not useful potassium is reclaimed, bring very big loss economically, in order to address this problem, No. 4060586 patents of the U.S. are separated potassium silicofluoride with the phosphoric acid/sulfuric acid extraction process from acid Jie gypsum, this recovery method is possible, but it wants heating and cooling in reclaiming technology, the complicated consumed energy of flow process is big, band acidity need be carried out three wastes processing in the final gypsum, unreasonable economically, so the recovery problem of potassium is never rationally solved in the fluorine-containing silicic acid syngenite, U.S.P4328196 is with K
2SiF
6Decompose with CaO, it is to adopt the raw material production KH different with the application's case
2PO
4
The objective of the invention is to adopt the calcium oxide potassium silicofluoride of indissoluble in the acid-mediated gypsum slurry again, to alkali solution, impel the potassium silicofluoride in sour Jie's gypsum to divide Jie and potassium silicofluoride and dihydrate gypsum to react completely in neutrality, generate potassium sulfate solution, pulp liquor (vitriolate of tartar) can return into acid medium system as the washings of sour Jie's gypsum again.
Design of the present invention is that sulfuric acid and Repone K react generation sal enixum and hydrogen chloride gas under 120～200 ℃ of temperature, the hydrogen chloride gas of overflowing absorbs through condensation or water can manufacture hydrochloric acid, the sal enixum and the sulfuric acid that generate are 60～85 ℃ in temperature together, solvent and solute weight ratio is under the condition of 2-5, acid Jie phosphorus ore obtains sour Jie's slip, acid Jie slip obtains P thereby wash after filtration
2O
518～26%(weight), K
2O5～7%(weight) contain KH
2PO
4Filtrate and be easy to filtering sour Jie's gypsum, because the fluorine that phosphorus ore component contains in reaction process, silicon and potassium ion reaction generate the very little potassium silicofluoride of molten Jie's degree and follow in acid Jie gypsum, potassium in the fluorine-containing silicic acid syngenite is difficult to be reclaimed with molten Jie's way, but potassium silicofluoride can divide Jie in neutrality to basic solution, and potassium silicofluoride can play subdivision Jie reaction with dihydrate gypsum, so the acid Jie gypsum after the washing can be used lime (CaO) potassium silicofluoride of indissoluble in the acid-mediated gypsum slurry more after filtration.K
2SiF
6+ CaSO
42H
2O+2CaO → 3CaF
2+ K
2SO
4+ SiO
2+ 2H
2O, the consumption of calcium oxide are 3～10%(weight of sour Jie's gypsum (butt)), the slip pH of acid-mediated gypsum slurry is controlled at 7～10 again, and starching temperature again is 40～80 ℃, starches 0.5～1 hour acting under the identical liquid-solid ratio condition with acid Jie again.Filter then, this moment gypsum strainability constant substantially, pulp liquor is the solution that contains vitriolate of tartar again, again pulp liquor except that the part return starch again system held starch again the operation liquid-solid ratio, part enters acid medium system as the washings of acid Jie gypsum, the washing of secondary reverse circulation.
When effect of the present invention is phosphorus ore direct method potassium dihydrogen phosphate making or potassium-ammonium phosphate, add calcium oxide in the potassium fluoride gypsum that generates, at neutrality potassium silicofluoride of indissoluble in the acid-mediated gypsum slurry again to the alkali solution, impel the potassium silicofluoride in sour Jie's gypsum to decompose, simple to operate, react completely, subsidiary material are cheap and easy to get, 90～95%(weight in can recovered acid Jie gypsum) potassium accounts for phosphorus ore direct method potassium dihydrogen phosphate making or potassium-ammonium phosphate and always throws potassium amount 14～24%(weight).Be generated as vitriolate of tartar owing to transform, therefore also utilized part SO in sour Jie's gypsum
2Thereby, can also reduce the sulfuric acid consumption that acid is situated between and reacts, used calcium oxide also to eliminate the residual acid pollution of sour Jie's gypsum simultaneously.
When being phosphorus ore direct method potassium dihydrogen phosphate making or potassium-ammonium phosphate, the accompanying drawing of this specification sheets generates potassium recovery technical process in the potassium fluoride gypsum.
Among the figure: reactor (1), sour Jie's groove (2), strainer (3), washer (4), starch device (5) again, strainer (6), washer (7), Repone K (8), sulfuric acid (9), hydrogenchloride (10), phosphorus ore (11), sal enixum (12), sulfuric acid (13), acid Jie's slip (14), filtrate (15), sour Jie's gypsum (16), calcium oxide (17), water (18), gypsum (19).
Be most preferred embodiment of the present invention below:
Embodiment 1, gets sour Jie's gypsum (butt) and contains K
2O2.19%(weight), F2.14%(weight) 72.34 grams, add and to wash and starch liquid 215.66 grams again and contain K
2O1.23%(weight), SO＜`; ; 3`〉1.114%(weight), add calcium oxide 3.6 gram simultaneously, be to stir in 9.4 o'clock to starch again 1 hour at 80 ℃, pH, filter then, gypsum washs through secondary circulation, obtains gypsum (butt) 79 grams at last, wherein contains remaining K
2O is a 0.083%(weight), K
2The total yield of O is a 95.86%(weight).
Embodiment 2, get sour Jie's gypsum (butt) and contain K
2O2.19%(weight), F2.14%(weight) 96.96 grams, add and to wash and starch liquid 289.04 grams again and contain K
2O1.088%(weight), adding calcium oxide 3.5 gram simultaneously, is to stir in 7.5 o'clock to starch 1 hour at 40 ℃, pH again, filters then, and gypsum washs through secondary circulation, obtains gypsum (butt) 100.6 grams at last, wherein contains remaining K
2O is a 0.052%(weight), K
2The total yield of O is a 97.56%(weight).
Claims (3)
1, generate the recovery technology of potassium in the fluorine-containing silicic acid syngenite when a kind of phosphorus ore direct method potassium dihydrogen phosphate making or potassium-ammonium phosphate, be phosphorus ore and sal enixum, sulfuric acid acid is situated between to react and obtains sour Jie's slip, acid Jie slip after filtration, wash the filtrate of phosphoric acid potassium dihydrogen and acid Jie gypsum of fluorine-containing potassium silicate, acid Jie gypsum after filtration, washing, feature of the present invention is that usefulness is 3～10%(weight of sour Jie's gypsum (butt) when the consumption of calcium oxide) time, the neutrality of pH=7～10 of acid Jie gypsum slip to the alkali solution again slurry decompose the potassium silicofluoride of indissoluble in sour Jie's gypsum, starching temperature again is 40～80 ℃, the slurry time is 0.5～1 hour again, and pulp liquor (vitriolate of tartar) enters acid medium system as washings again.
2, reclaim technology according to the described potassium of claim 1, it is characterized in that: the consumption of optimum oxidation calcium is 3.6～5%(weight of sour Jie's gypsum (butt)).
3, reclaim technology according to the described potassium of claim 1, it is characterized in that: pH=7.5～9.4 of the slip of best acid-mediated gypsum slurry again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100438A CN85100438B (en) | 1985-04-01 | 1985-04-01 | Process for recovering potssium form k2sif6-bearing gypsum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100438A CN85100438B (en) | 1985-04-01 | 1985-04-01 | Process for recovering potssium form k2sif6-bearing gypsum |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85100438A CN85100438A (en) | 1986-07-02 |
| CN85100438B true CN85100438B (en) | 1988-12-21 |
Family
ID=4791157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85100438A Expired CN85100438B (en) | 1985-04-01 | 1985-04-01 | Process for recovering potssium form k2sif6-bearing gypsum |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85100438B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628003B (en) * | 2015-02-02 | 2017-03-15 | 嘉应学院 | A kind of method that utilization sodium permanganate production waste residue produces potassium fluosilicate |
| CN106278388A (en) * | 2016-08-12 | 2017-01-04 | 吉林万通集团有限公司 | Potassium-ammonium phosphate |
-
1985
- 1985-04-01 CN CN85100438A patent/CN85100438B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85100438A (en) | 1986-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1962421B (en) | Phosphorite acidolysis method | |
| CN102417169B (en) | Acidolysis method of magnesium-containing phosphate rock | |
| RU2337879C1 (en) | Method for processing phosphogypsum, containing phosphorous compound and lanthanides | |
| US3551332A (en) | Purification of fluorine-containing industrial waste waters | |
| CN101337657A (en) | Process for disassembling phosphate ore by mixed acid and coproducing potassium dihydrogen phosphate, hydrogen phosphate and combined fertilizer | |
| US5427757A (en) | Process for the production of phosphoric acid and hydrogen fluoride from phosphate rock and fluosilicic acid | |
| CN101175691A (en) | Process for producing high purity phosphates | |
| US3966877A (en) | Method of processing of waste gases | |
| US3792151A (en) | Process for producing phosphoric acid | |
| US4160012A (en) | Process of refining sodium hexafluorosilicate containing gypsum | |
| CN101434386A (en) | Method for producing fine phosphate by using dilute acid to decompose middle and low grade phosphate ore using | |
| US3615195A (en) | Fluosilic acid recovery | |
| US4861490A (en) | Removal of cationic impurities from inorganic solutions | |
| CN105819452B (en) | A kind of method that fluorine resource is reclaimed in the defluorination residues from feed phosphate | |
| US4435370A (en) | Preparation of monocalcium phosphate and/or phosphoric acid from phosphate rock | |
| CN105271157B (en) | A kind of method of integrated treatment titanium white waste acid and phosphate ore flotation tailings | |
| US4222990A (en) | Production of fluoride-free phosphates | |
| US4160657A (en) | Preparation of monocalcium phosphate and phosphoric acid | |
| US4060586A (en) | Recovery of fluorides from gypsum | |
| US4086322A (en) | Production of fluoride-free phosphates | |
| CN105819415B (en) | A kind of production method for the full utilization of resources of phosphorus ore that hydrochloric acid produces calcium hydrogen phosphate fodder | |
| US4067957A (en) | Process for producing hydrogen fluoride from an aqueous hydrofluorosilicic acid solution | |
| CN85100438B (en) | Process for recovering potssium form k2sif6-bearing gypsum | |
| CN101786741A (en) | Method for defluorinating acid waste water with high fluorine | |
| CN111392754B (en) | Method and equipment for purifying calcium chloride from fluorine-containing solid waste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| CI01 | Correction of invention patent gazette |
Correction item: Classification number Correct: C01D7/04 False: C01C7/04 Number: 7 Page: 23 Volume: 2 |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ERR | Gazette correction |
Free format text: CORRECT FROM: C01C7/04 TO: C01D7/04 |
|
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |