CN106115742B - A kind of technique of two step method Cycle-decomposition trans-utilization ardealite - Google Patents
A kind of technique of two step method Cycle-decomposition trans-utilization ardealite Download PDFInfo
- Publication number
- CN106115742B CN106115742B CN201610444888.7A CN201610444888A CN106115742B CN 106115742 B CN106115742 B CN 106115742B CN 201610444888 A CN201610444888 A CN 201610444888A CN 106115742 B CN106115742 B CN 106115742B
- Authority
- CN
- China
- Prior art keywords
- electrodialysis
- ardealite
- level
- room
- calcium
- 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 - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/06—Preparation of sulfates by double decomposition
- C01D5/10—Preparation of sulfates by double decomposition with sulfates of magnesium, calcium, strontium, or barium
-
- 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
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
-
- 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
- C01F11/16—Purification
Abstract
The invention belongs to ardealite technical field of comprehensive utilization, and in particular to a kind of technique of two step method Cycle-decomposition trans-utilization ardealite.The technique includes：Decomposing ardealite is converted into sodium sulphate and calcium hydroxide by the first step, sodium hydroxide solution and ethanol are added i.e. in ardealite raw material, reacted under the conditions of stirring at normal temperature, after reaction terminates, by settling and filtering carry out separation of solid and liquid, metabisulfite solution and calcium slag are obtained, using stage division, calcium hydroxide in calcium slag is separated with other impurity components, obtains Ca (OH)2The calcium hydroxide product of content >=90%, residual impurity can be used as the dispensing or building material of cement processed；Second step utilizes three stage countercurrent bipolar membrane electrodialysis systems, metabisulfite solution is converted into sulfuric acid and sodium hydroxide solution, sodium hydroxide solution is circularly used for decomposition and inversion ardealite, and sulfuric acid is circularly used for decomposing phosphate rock phosphoric acid.
Description
Technical field
The invention belongs to ardealite technical field of comprehensive utilization, and in particular to a kind of two step method Cycle-decomposition trans-utilization phosphorus
The technique of gypsum.
Background technology
Phosphatic fertilizer company produces high concentration phosphate fertilizer and composite fertilizer, typically all with sulfuric acid decomposition phosphorus ore phosphoric acid, then with phosphoric acid system
High concentration phosphate fertilizer and composite fertilizer.When with sulfuric acid decomposition phosphorus ore, phosphorus ore containing and sulfuric acid reaction in phosphorus ore, phosphoric acid and difficulty are generated
Dissolubility ardealite (CaSO4·xH2O).The common impure mineral of some in phosphorus ore, such as calcite and dolomite also can be with sulfuric acid
Reaction generation ardealite.
Ca5(PO4)3F+5H2SO4+5xH2O→5CaSO4·xH2O+3H3PO4+HF↑
CaCO3+H2SO4+(x-1)H2O→CaSO4·xH2O+CO2↑
CaMg(CO3)2+2H2SO4+(x-2)H2O→MgSO4+CaSO4·xH2O+2CO2↑
The main chemical reactions of phosphoric acid processed more than, often produce 1 ton of phosphoric acid, at least to consume 1.7 tons of sulfuric acid, simultaneously
The ardealite that more than 3 tons of output.Phosphatic fertilizer company will not only take a large amount of all using the method processing ardealite of stockpiling for a long time
Land resource, it is possible to cause environmental pollution, can also take over the land for use to manufacturing enterprise and build stockyard and bring very big financial burden.
As a kind of chemical gypsum, ardealite is different from the natural gypsum, and the impurity component contained by it can be applied to performance
Produce considerable influence.For example, the acid waste water in ardealite not only has corrosivity, and phosphate anion is attached to gypsum table
Face, the intensity of product after gypsum sets speed and hardening can be reduced；The presence of fluoride, gypsum product can be made to be easy to weathering, by force
Degree reduces；The presence of organic matter, the color and luster and intensity of plastering can be had an impact.Therefore, ardealite is typically passed through
Pretreatment, its acidity is neutralized, after removing objectionable impurities therein, preferable application performance could be obtained.But pretreated phosphorus
Gypsum is compared with natural gypsum ore deposit, either in terms of performance or processing cost, often all difficult competitive superiority.
Ardealite is converted into other chemical products, is the effective way of ardealite comprehensive utilization.Existing technique includes
With ardealite Sulphuric acid co-producing cement, ardealite is converted into ammonium sulfate, potassium sulfate and other sulfide etc..Although these techniques
Technical comparative maturity, but there is the problems such as comprehensive utilization cost is higher, and products obtained therefrom market demand is little for practical application.
Solve the realistic problem of ardealite recycling, it is new there is an urgent need to seek from technology, cost and product market etc.
Break through.
The content of the invention
The present invention is in view of the shortcomings of the prior art, and it is an object of the present invention to provide a kind of two step method Cycle-decomposition trans-utilization ardealite
Technique, to solve ardealite comprehensive utilization cost higher, the problem of conversion product market demand is little.
For achieving the above object, the technical solution adopted by the present invention is：
A kind of technique of two step method Cycle-decomposition trans-utilization ardealite, comprises the following steps：
(1) sodium hydroxide solution and ethanol are added in ardealite raw material, is reacted under the conditions of stirring at normal temperature, reaction knot
Shu Hou, by settling and filtering carry out separation of solid and liquid, obtain metabisulfite solution and calcium slag；
(2) stage division is used, the calcium hydroxide in calcium slag is separated with other impurity components, obtains Ca (OH)2Content
>=90% calcium hydroxide product, residual impurity can be used as the dispensing or building material of cement processed；
(3) three stage countercurrent bipolar membrane electrodialysis systems are utilized, metabisulfite solution is converted into sulfuric acid and sodium hydroxide solution；
(4) sodium hydroxide solution is circulated for decomposition and inversion ardealite, sulfuric acid is circulated for decomposing phosphate rock phosphoric acid.
In such scheme, the content of calcium sulfate is 70wt%~90wt% in the ardealite, the matter of the sodium hydroxide
It is 8~10% to measure concentration, and the mol ratio of the sodium hydroxide and calcium sulfate is 2~2.4：1, the ethanol consumption is ardealite matter
The 0.2wt% of amount..
In such scheme, the reaction time of step (1) described reaction is 10~30min, and the mixing speed is 5~10m/
s。
In such scheme, the particle diameter of calcium hydroxide is less than 20 μm in the calcium slag.
In such scheme, in the three stage countercurrents bipolar membrane electrodialysis system, at the beginning of the sodium sulphate of first order electrodialysis salt room
Beginning mass concentration is 14~16%, and the initial liquid of sour room and alkali room is the acid solution and alkali lye obtained after the electrodialysis of the second level；First
The mass concentration of sodium sulphate is down to 5~7% after level electrodialysis, into second level electrodialysis salt room, sour room in the electrodialysis of the second level
Initial liquid with alkali room is the acid solution and alkali lye that are obtained after third level electrodialysis, gained acid solution and alkali lye point after the electrodialysis of the second level
Do not return to the electrodialytic sour room of the first order and alkali room；The mass concentration of sodium sulphate is down to 1~2% after the electrodialysis of the second level, enters
Third level electrodialysis salt room, gained acid solution and alkali lye return to the electrodialytic sour room in the second level and alkali respectively after third level electrodialysis
Room；The mass concentration of sodium sulphate is down to less than 0.7% after third level electrodialysis, can be used as third level electrodialysis alkali room or sour room
Initial liquid.
In such scheme, the electrodialytic current density of the first order is 20~40mA/cm2；The second level electrodialysis
Current density be 10~20mA/cm2；The electrodialytic current density of the third level is 5~15mA/cm2。
In such scheme, the H of gained acid solution after the first order electrodialysis2SO4Mass concentration is 13~15%, gained alkali
The NaOH mass concentrations of liquid are 8~10%, and wherein alkali lye can be directly used for step (1) the decomposing ardealite conversion reaction, acid
The absorbing liquid that liquid can be used as sulfuric acid plant produces industrial sulphuric acid, eventually for decomposing phosphate rock phosphoric acid.
Decomposing ardealite is converted into metabisulfite solution in the present invention and the reaction equation of calcium slag is as follows,
2NaOH+CaSO4·xH2O→Na2SO4+Ca(OH)2↓+xH2O
The mass content of calcium sulfate is generally 70%~90% in ardealite.According to the calcium sulphate content of actual measurement, press more than
The mol ratio of chemical reaction calculates, and can obtain the sodium hydroxide theoretical amount needed for decomposition and inversion ardealite.Actual decomposition and inversion
The sodium hydroxide concentration of ardealite is 1~1.2 times of theoretical amount, and the method that substep can be used to add sodium hydroxide,
As first by the mol ratio 1 of calcium sulfate and sodium hydroxide:2 add sodium hydroxide solution, after reacting a period of time, add excessive hydrogen
Sodium oxide molybdena.
The effect that ethanol is added in the present invention is in order to promote calcium hydroxide to form small grains (being less than 20 μm), to adopt
With the method for classification, by the calcium hydroxide in calcium slag and other impurity components (such as quartz, aluminate and unreacted calcium sulfate
Deng) separation, obtain Ca (OH)2The calcium hydroxide product (account for calcium slag 60~80%) of content >=90%, it is remaining for matter it is miscellaneous into
Divide (account for calcium slag 20~40%), can be used as dispensing or building material of cement processed etc..
Beneficial effects of the present invention are as follows：
(1) all chemical reagent reusable edibles in the present invention, the atom economy of whole phosphoric acid by wet process process can be achieved,
The cost of material of decomposing phosphate rock and ardealite is greatly lowered；
(2) decomposing ardealite conversion of the present invention can be carried out quickly at normal temperatures, and process is easily controlled, and energy consumption is relatively low；
(3) present invention process does not have " three wastes " problem, belongs to green energy-saving and emission-reducing technique；Conversion is also not present simultaneously
The market demand problem of products obtained therefrom.
Brief description of the drawings
Fig. 1 is the two step method Cycle-decomposition trans-utilization ardealite process schematic representation of the present invention.
Fig. 2 is the principle schematic using bipolar membrane electrodialysis system Sodium Sulfate Electrodialysis solution.
Fig. 3 is three stage countercurrent bipolar membrane electrodialysis process schematic representations.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Raw material is the ardealite of Yunnan Linhua Group Corp., Ltd. in the embodiment of the present invention, through its main component of chemical analysis
For：CaO 30.40wt%, P2O50.64wt%, SiO27.13wt%, MgO 0.09wt%, Al2O30.62wt%, Fe2O3
0.25wt%, SO342.45wt%, crystallization water 17.35wt%.It can be seen that：Wherein CaSO4Content be 72.17wt%.It is main
The content for wanting impurity component quartz is 7.13wt%.
Embodiment 1
A kind of technique of two step method Cycle-decomposition trans-utilization ardealite, comprises the following steps：
(1) NaOH solution by concentration for 9.16wt%, by sodium hydroxide and CaSO4Theoretical molar dosage needed for reaction
2:1, it is added in the reactor for filling ardealite raw material；Ethanol is added by the 0.2wt% of phosphogypsum quality proportioning simultaneously,
At room temperature with 6.3m/s mixing speed, stirring reaction 10min；Then slowly add again excessive NaOH solution (sodium hydroxide
Mole is CaSO40.15 times of mole), continue stirring reaction 5min.Then stop stirring, by slurry supernatant and filter,
Filter residue countercurrent washing is secondary, obtains the Na that mass concentration is 15.03%2SO4Solution and calcium slag, CaSO4Rates of decomposing and transforming is
96.25%.Calcium slag separates less than 20 μm grades by hydraulic classiciation, obtains Ca (OH)2Content is 90.36wt% product, is produced
Rate is 72.62%；
Using three stage countercurrent bipolar membrane electrodialysis systems, metabisulfite solution is converted into sulfuric acid and sodium hydroxide solution, it is double
The principle schematic of pole EDBM system Sodium Sulfate Electrodialysis solution is shown in Fig. 2, the signal of three stage countercurrent bipolar membrane electrodialysis techniques
Figure is shown in Fig. 3；Each operation relevant operating parameter of electrodialysis is as shown in the table.
The electrodialysis running parameter list of table 1
After electrodialysis, 96.59wt% sodium sulphate is converted into sulfuric acid and sodium hydroxide in original metabisulfite solution, always
Electrodialysis energy consumption be 0.938kwh/1kg sodium sulphate.Salt room is only remained in original metabisulfite solution after three-stage electrodialysis
3.11wt% sodium sulphate, decomposing ardealite operation, one-level bipolar membrane electrodialysis system electrodialysis are mainly returned to by alkali room liquid
The H of gained acid solution afterwards2SO4Mass concentration is 13.22%, and the NaOH mass concentrations of gained alkali lye are 9.62%, and wherein alkali lye can be straight
Connecing and return to decomposing ardealite step of converting described in step (1), the absorbing liquid that acid solution can be used as sulfuric acid plant produces industrial sulphuric acid,
Eventually for decomposing phosphate rock phosphoric acid, whole technical process does not have waste liquid generation.The quality of sodium sulphate is dense after third level electrodialysis
Degree is down to 0.6%, and the overwhelming majority can be used as the initial liquid of third level bipolar membrane electrodialysis system alkali room, is used as third level acid on a small quantity
A small amount of sodium sulphate electrolyte is returned in the initial liquid of room, third level electrodialysis sour room and the initial liquid of alkali room, electrodialysis can be promoted
The flowing of initial period electric current, it is favourable to electrodialytic process.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change or change therefore amplified
Move within still in the protection domain of the invention.
Claims (6)
1. a kind of technique of two step method Cycle-decomposition trans-utilization ardealite, it is characterised in that comprise the following steps：
（1）Sodium hydroxide solution and ethanol are added in ardealite raw material, is reacted under the conditions of stirring at normal temperature, reaction terminates
Afterwards, by settling and filtering carry out separation of solid and liquid, metabisulfite solution and calcium slag are obtained；The quality of calcium sulfate contains in the ardealite
Measure as 70wt%~90wt%, the mass concentration of the sodium hydroxide solution is 8 ~ 10%, mole of the sodium hydroxide and calcium sulfate
Than for 2 ~ 2.4：1；The sodium hydroxide solution substep adds；
（2）Using stage division, the calcium hydroxide in calcium slag is separated with other impurity components, obtains the hydrogen-oxygen of content >=90%
Change calcium product, residual impurity is used as the dispensing or building material of cement processed；
（3）Using three stage countercurrent bipolar membrane electrodialysis systems, metabisulfite solution is converted into sulfuric acid and sodium hydroxide solution；It is described
In three stage countercurrent bipolar membrane electrodialysis systems, the sodium sulphate initial mass concentration of first order electrodialysis salt room is 14 ~ 16%, sour room
It is the acid solution and alkali lye that obtain after the electrodialysis of the second level with the initial liquid of alkali room；The mass concentration of sodium sulphate after first order electrodialysis
5 ~ 7% are down to, into second level electrodialysis salt room, the initial liquid of sour room and alkali room is third level electrodialysis in the electrodialysis of the second level
The acid solution and alkali lye obtained afterwards, gained acid solution and alkali lye return to the electrodialytic sour room of the first order and alkali respectively after the electrodialysis of the second level
Room；The mass concentration of sodium sulphate is down to 1 ~ 2% after the electrodialysis of the second level, into third level electrodialysis salt room, after third level electrodialysis
Gained acid solution and alkali lye return to the electrodialytic sour room in the second level and alkali room respectively；The mass concentration of sodium sulphate after third level electrodialysis
Less than 0.7% is down to, the initial liquid as third level electrodialysis alkali room or sour room；
（4）Sodium hydroxide solution is circulated for decomposition and inversion ardealite, sulfuric acid is circulated for decomposing phosphate rock phosphoric acid.
2. technique according to claim 1, it is characterised in that the ethanol consumption is the 0.2wt% of phosphogypsum quality.
3. technique according to claim 1, it is characterised in that step（1）The reaction time of the reaction is 10 ~ 30min,
The mixing speed of the stirring is 5 ~ 10m/s.
4. technique according to claim 1, it is characterised in that the particle diameter of calcium hydroxide is less than 20 μm in the calcium slag.
5. technique according to claim 1, it is characterised in that the electrodialytic current density of the first order is 20 ~ 40mA/
cm2；The electrodialytic current density in the second level is 10 ~ 20mA/cm2；The electrodialytic current density of the third level be 5 ~
15mA/cm2。
6. technique according to claim 1, it is characterised in that the mass concentration of gained acid solution is 13 after first order electrodialysis
~ 15%, the mass concentration of gained alkali lye is 8 ~ 10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610444888.7A CN106115742B (en) | 2016-06-20 | 2016-06-20 | A kind of technique of two step method Cycle-decomposition trans-utilization ardealite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610444888.7A CN106115742B (en) | 2016-06-20 | 2016-06-20 | A kind of technique of two step method Cycle-decomposition trans-utilization ardealite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106115742A CN106115742A (en) | 2016-11-16 |
| CN106115742B true CN106115742B (en) | 2017-11-21 |
Family
ID=57470947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610444888.7A Expired - Fee Related CN106115742B (en) | 2016-06-20 | 2016-06-20 | A kind of technique of two step method Cycle-decomposition trans-utilization ardealite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106115742B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106698497B (en) * | 2017-01-22 | 2018-05-01 | 武汉工程大学 | A kind of method that calcium sulfate is prepared by ardealite |
| CN109437121B (en) * | 2018-11-06 | 2022-04-12 | 宜宾海丝特纤维有限责任公司 | Multistage treatment method for viscose sodium sulfate waste liquid |
| CN110102559B (en) * | 2019-04-29 | 2020-05-19 | 长江师范学院 | Method for synergistically stabilizing and curing phosphogypsum and phosphorite flotation tailings |
| CN115010161B (en) * | 2022-01-19 | 2024-01-05 | 昆明理工大学 | Method for converting waste gypsum into alpha semi-hydrated gypsum |
| CN115155317A (en) * | 2022-07-12 | 2022-10-11 | 杭州匠容道环境科技有限公司 | Treatment process for recycling phosphoric acid by using phosphogypsum |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898773A (en) * | 2010-02-11 | 2010-12-01 | 汪晋强 | Method for preparing sodium sulfate, bleaching powder and calcium chloride from phosphogypsum |
| CN103232052A (en) * | 2013-05-20 | 2013-08-07 | 昆明理工大学 | Method for preparing high-purity calcium carbonate directly from phosphogypsum |
| CN104828784A (en) * | 2015-04-29 | 2015-08-12 | 武汉工程大学 | Process for preparation of acid and combined production of cement through suspension decomposition of phosphogypsum out of kiln |
-
2016
- 2016-06-20 CN CN201610444888.7A patent/CN106115742B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898773A (en) * | 2010-02-11 | 2010-12-01 | 汪晋强 | Method for preparing sodium sulfate, bleaching powder and calcium chloride from phosphogypsum |
| CN103232052A (en) * | 2013-05-20 | 2013-08-07 | 昆明理工大学 | Method for preparing high-purity calcium carbonate directly from phosphogypsum |
| CN104828784A (en) * | 2015-04-29 | 2015-08-12 | 武汉工程大学 | Process for preparation of acid and combined production of cement through suspension decomposition of phosphogypsum out of kiln |
Non-Patent Citations (3)
| Title |
|---|
| 双极膜电渗析清洁制备NaOH 和H2SO4的试验研究;高艳荣等;《水处理技术》;20131031;第39卷(第10期);第18-26页 * |
| 氧化钙基吸附剂的制备及其CO2吸附性能研究;沈辉;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20150315(第03期);第32-33页，第64页 * |
| 电渗析硫酸钠的试验研究;鲁顺利等;《云南冶金》;20041231;第33卷(第6期);第19-21页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106115742A (en) | 2016-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106115742B (en) | A kind of technique of two step method Cycle-decomposition trans-utilization ardealite | |
| CN102534187B (en) | Method for treating pyrite cinder by combining acidic leaching with alkaline dissolving | |
| CN101607834A (en) | Utilize potassium-bearing mineral, phosphogypsum and high sulphur coal to prepare the method for potash fertilizer and co-producing sulfuric acid | |
| CN103145148B (en) | A kind of method of ammonia solution system strengthening calcium base solid waste mineralising stabilizing carbon dioxide | |
| CN101555033B (en) | Method for preparing cryolite and coproducing soluble glass by using hydrof luorosilicic acid | |
| CN104096707B (en) | Semi-dry desulphurization ash resource utilization method | |
| CN102383179B (en) | A kind of method that industrial waste acid and phosphogypsum fully utilize | |
| CN104211099B (en) | Resource recycling method of industrial phosphogypsum waste residues | |
| CN107879363A (en) | A kind of method that nitric acid decomposes phosphorus mine tailing extracting sulfuric acid calcium pyroborate by-product magnesium hydroxide and ammonium nitrate magnesium | |
| CN110002415A (en) | A method of phosphate radical and sulfate radical are recycled from ferric phosphate production waste water | |
| CN103073034B (en) | Method for removing magnesium from ultralow-quality phosphate rock and producing magnesium hydroxide | |
| CN101850992A (en) | Method for preparing calcium carbonate and co-producing sodium sulfate by using phosphorus gypsum and soda ash | |
| CN109179476B (en) | Method for controlling water content of titanium gypsum | |
| CN100415639C (en) | Process for reductive decomposition of phosphogypsum by sulfur coal | |
| CN104495774A (en) | Method for co-production of nanometer hydroxyapatite and calcium sulfate whisker from phosphogypsum | |
| CN102424426B (en) | Method for preparing iron oxide red and sodium phosphate by using yellow phosphorus by-product phosphor-iron slag | |
| CN104386713B (en) | A kind of method of Repone K and ammonium sulfate preparing potassium sulfate | |
| CN101434386A (en) | Method for producing fine phosphate by using dilute acid to decompose middle and low grade phosphate ore using | |
| CN101643204A (en) | Novel process for cleanly producing phosphate ammoniate fertilizer in the processing of phosphate rock powder | |
| CN104211104A (en) | Separation and recovery method of thermal coal power plant flue gas desulfurization gypsum waste residues | |
| CN101323452A (en) | Method for preparing precipitated silica with boron sludge | |
| CN100519416C (en) | Method for producing basic magnesium carbonate by using boron magnesium fertilizer with coproduction of nano magnesium oxide | |
| CN106830416A (en) | A kind of method that guanite precipitation method process desulfurization wastewater | |
| CN104788131A (en) | Method for producing superphosphate by utilizing low-grade phosphate ore mixed acid process | |
| CN101823747B (en) | Method for producing precipitated calcium carbonate and white carbon black and coproducing sodium chloride and powdered carbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171121 Termination date: 20200620 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |