CN113336242A - Preparation method of phosphogypsum solid-phase ball milling of ammonium sulfate for water treatment - Google Patents
Preparation method of phosphogypsum solid-phase ball milling of ammonium sulfate for water treatment Download PDFInfo
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910052921 ammonium sulfate Inorganic materials 0.000 title claims abstract description 114
- 235000011130 ammonium sulphate Nutrition 0.000 title claims abstract description 113
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 65
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000000498 ball milling Methods 0.000 title claims abstract description 27
- 239000007790 solid phase Substances 0.000 title claims abstract description 27
- 239000000047 product Substances 0.000 claims abstract description 36
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 32
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 32
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 32
- 238000000746 purification Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000013067 intermediate product Substances 0.000 claims abstract description 19
- 239000011521 glass Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000007605 air drying Methods 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 230000008020 evaporation Effects 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 8
- 208000012839 conversion disease Diseases 0.000 abstract description 7
- 238000000034 method Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052602 gypsum Inorganic materials 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000010440 gypsum Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007255 decyanation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/244—Preparation by double decomposition of ammonium salts with sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention discloses a phosphogypsum solid-phase ball-milling preparation method of ammonium sulfate for water treatment, which comprises the following steps: weighing a certain amount of phosphogypsum, ammonium bicarbonate and glass balls, adding the glass balls into a ball mill, and starting the ball mill; adding phosphogypsum and ammonium bicarbonate into a ball mill for reaction, separating the materials from the ball mill after the reaction is finished, and air-drying the materials to obtain an ammonium sulfate primary product A; and performing primary purification on the ammonium sulfate primary product A to obtain an ammonium sulfate intermediate product B, and finally performing secondary purification on the ammonium sulfate intermediate product B to obtain a finished product of ammonium sulfate. The phosphogypsum solid-phase ball-milling preparation method of ammonium sulfate for water treatment is safe and environment-friendly, has high reaction conversion rate, and the prepared finished product of ammonium sulfate has high nitrogen content and high purity of ammonium sulfate, and is suitable for water treatment and disinfection of water works.
Description
Technical Field
The invention belongs to the technical field of ammonium sulfate preparation, and particularly relates to a phosphogypsum solid-phase ball-milling preparation method of ammonium sulfate for water treatment.
Background
Because chloramine (combined chlorine) disinfection has the advantages of good stability, long duration in a pipe network, capability of effectively controlling the propagation of harmful microorganisms and the formation of a biological membrane in the pipe network, strong sterilization durability and the like, the chloramine (combined chlorine) disinfection is widely applied to water plants at present. Under the condition of the cross-bottom of the ammonia nitrogen content of raw water, the water plant can add liquid ammonia into the raw water to improve the ammonia nitrogen content of the raw water, and the liquid ammonia reacts with chlorine disinfectant to generate chloramine, so that compound chlorine is formed for disinfection, and the liquid ammonia is transported. The ammonia water is firstly hydrolyzed to generate ammonia water, and then reacts with the chlorine disinfectant sodium hypochlorite to form chloramine.
Patent CN108483463A discloses a method for preparing high-quality ammonium sulfate by using coking desulfurization decyanation waste liquid, which specifically comprises the following steps: firstly, regulating pH value by aid of an auxiliary agent, adding a decoloring agent for decoloring, then adding a crystal habit modifier, evaporating and concentrating, controlling the concentration sum of ammonium thiocyanate and ammonium thiosulfate to be 60-80%, crystallizing and separating out all ammonium sulfate, separating out and removing impurities, separating out ammonium sulfate crystals, rinsing the ammonium sulfate crystals by ammonium persulfate saturated solution, and thus obtaining high-purity ammonium sulfate. Patent CN105439174B discloses a preparation method of ammonium sulfate, which specifically comprises the following steps: 93% concentrated sulfuric acid absorbs ammonia gas generated by urea cracking in the cyanuric acid production process to form ammonium sulfate suspension, and the ammonium sulfate suspension is crystallized, centrifuged and dried to obtain a product ammonium sulfate.
Therefore, the above problems need to be solved.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects, the invention aims to provide the phosphogypsum solid-phase ball-milling preparation method of the ammonium sulfate for water treatment, which is safe and environment-friendly, has high reaction conversion rate, and the prepared finished product of the ammonium sulfate has high nitrogen content and high purity, and is suitable for water treatment and disinfection of water works.
The technical scheme is as follows: in order to realize the aim, the invention provides a phosphogypsum solid-phase ball-milling preparation method of ammonium sulfate for water treatment, which comprises the following steps: weighing a certain amount of phosphogypsum, ammonium bicarbonate and glass balls, adding the glass balls into a ball mill, and starting the ball mill; adding phosphogypsum and ammonium bicarbonate into a ball mill for reaction.
Further, the phosphogypsum solid-phase ball-milling preparation method of the ammonium sulfate for water treatment further comprises the following steps: and after the reaction is finished, separating the materials from the ball mill, and air-drying the materials to obtain an ammonium sulfate primary product A.
Further, in the preparation method of the phosphogypsum solid-phase ball milling of the ammonium sulfate for water treatment, CaSO in the phosphogypsum is4·2H2The molar ratio of O to ammonium bicarbonate is 0.55-0.60.
Further, in the preparation method of the phosphogypsum solid-phase ball milling of the ammonium sulfate for water treatment, the reaction time is 10-20 min.
Further, in the preparation method of the phosphogypsum solid-phase ball milling of the ammonium sulfate for water treatment, the mass ratio of the total mass of the phosphogypsum and the ammonium bicarbonate to the glass balls is 1: 3-1: 5.
Further, in the preparation method of the phosphogypsum solid-phase ball milling of the ammonium sulfate for water treatment, the rotating speed of the ball mill is 600-800 r/min.
Further, the phosphogypsum solid-phase ball-milling preparation method of the ammonium sulfate for water treatment further comprises a primary purification step: washing the ammonium sulfate primary product A with distilled water, filtering, concentrating, crystallizing and drying the filtrate to obtain an ammonium sulfate intermediate product B.
Further, the phosphogypsum solid-phase ball-milling preparation method of the ammonium sulfate for water treatment further comprises a secondary purification step: mixing the ammonium sulfate intermediate product B and water according to the mass ratio of 1:1.5 to obtain a mixed solution C, putting the mixed solution C into a crystallizer, adding sodium sulfate accounting for 0.85% of the mixed solution C by mass, heating to 60 ℃, preserving heat and fully stirring to completely dissolve solids; then adding ammonium sulfate seed crystal which accounts for 5.5 percent of the mass fraction of the mixed solution C, carrying out reduced pressure evaporation at 25 ℃, maintaining the vacuum degree in a crystallizer at 0.08Mpa, stopping reduced pressure evaporation after the evaporated water amount reaches 75 percent of the weight of the added water, carrying out temperature-controlled cooling at the cooling rate of 4 ℃/h, stopping cooling when the temperature is reduced to 9 ℃, carrying out crystal growth for 2.5h, filtering, washing and drying to obtain the finished product of ammonium sulfate.
The technical scheme shows that the invention has the following beneficial effects: the phosphogypsum solid-phase ball-milling preparation method of the ammonium sulfate for water treatment is safe and environment-friendly, the reaction conversion rate is as high as 99.75%, the nitrogen content of the prepared finished product of the ammonium sulfate is as high as 21.17%, the purity of the ammonium sulfate is as high as 99.8%, and the method is suitable for water treatment disinfection of water plants and is specifically analyzed as follows:
1. the preparation of ammonium sulfate by phosphogypsum is based on the following chemical reaction:
CaSO4·2H2O+2NH4HCO3＝(NH4)2SO4+CaCO3+CO2+3H2O (Ⅰ)
the method takes phosphogypsum and ammonium bicarbonate as raw materials, prepares ammonium sulfate through solid-phase reaction, does not need heating, can be carried out at normal temperature, has short reaction time, high conversion rate and large material handling capacity, can realize continuous production, and has low energy consumption and large yield.
2. The raw materials of the phosphogypsum industrial waste residue are rich, cheap and easily available, ammonium bicarbonate is relatively expensive, and the reaction is facilitated by increasing the concentration of reactants, so that the phosphogypsum is slightly excessive, namely CaSO in the phosphogypsum4·2H2When the molar ratio of O to ammonium bicarbonate is 0.55-0.60, the reaction conversion rate is high.
3. Besides containing ammonium sulfate, impurities such as calcium carbonate, ammonium gypsum, a small amount of gypsum and the like exist in the ammonium sulfate primary product A, through the primary purification step, the ammonium sulfate in the ammonium sulfate primary product A can be dissolved, the ammonium gypsum is decomposed into ammonium sulfate and gypsum, the calcium carbonate and the gypsum are left in filter residues, and an ammonium sulfate intermediate product B after primary purification is obtained.
4. The ammonium sulfate intermediate product B is further purified again through further secondary, further gets rid of through the impurity of crystallization in with ammonium sulfate intermediate product B, has added the sodium sulfate simultaneously, wherein contains the sulfate radical for the crystallization rate accelerates, and the purity of finished product ammonium sulfate obtains further improvement.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the following embodiments and specific experimental data, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of phosphogypsum solid-phase ball milling of ammonium sulfate for water treatment comprises the following steps: weighing a certain amount of phosphogypsum, ammonium bicarbonate and glass balls, adding the glass balls into a ball mill, and starting the ball mill; adding phosphogypsum and ammonium bicarbonate into a ball mill for reaction.
Further, the method also comprises the following steps: and after the reaction is finished, separating the materials from the ball mill, and air-drying the materials to obtain an ammonium sulfate primary product A.
Wherein, the CaSO in the phosphogypsum4·2H2The molar ratio of O to ammonium bicarbonate was 0.55.
And the reaction time was 10 min.
And the mass ratio of the total mass of the phosphogypsum and the ammonium bicarbonate to the glass spheres is 1: 3.
And the rotating speed of the ball mill is 600 r/min.
Further, the method also comprises a primary purification step: washing the ammonium sulfate primary product A with distilled water, filtering, concentrating, crystallizing and drying the filtrate to obtain an ammonium sulfate intermediate product B.
Still further, the method also comprises a secondary purification step: mixing the ammonium sulfate intermediate product B and water according to the mass ratio of 1:1.5 to obtain a mixed solution C, putting the mixed solution C into a crystallizer, adding sodium sulfate accounting for 0.85% of the mixed solution C by mass, heating to 60 ℃, preserving heat and fully stirring to completely dissolve solids; then adding ammonium sulfate seed crystal which accounts for 5.5 percent of the mass fraction of the mixed solution C, carrying out reduced pressure evaporation at 25 ℃, maintaining the vacuum degree in a crystallizer at 0.08Mpa, stopping reduced pressure evaporation after the evaporated water amount reaches 75 percent of the weight of the added water, carrying out temperature-controlled cooling at the cooling rate of 4 ℃/h, stopping cooling when the temperature is reduced to 9 ℃, carrying out crystal growth for 2.5h, filtering, washing and drying to obtain the finished product of ammonium sulfate.
Example 2
A preparation method of phosphogypsum solid-phase ball milling of ammonium sulfate for water treatment comprises the following steps: weighing a certain amount of phosphogypsum, ammonium bicarbonate and glass balls, adding the glass balls into a ball mill, and starting the ball mill; adding phosphogypsum and ammonium bicarbonate into a ball mill for reaction.
Further, the method also comprises the following steps: and after the reaction is finished, separating the materials from the ball mill, and air-drying the materials to obtain an ammonium sulfate primary product A.
Wherein, the CaSO in the phosphogypsum4·2H2The molar ratio of O to ammonium bicarbonate was 0.60.
And the reaction time was 20 min.
And the mass ratio of the total mass of the phosphogypsum and the ammonium bicarbonate to the glass spheres is 1: 5.
And the rotation speed of the ball mill is 800 r/min.
Further, the method also comprises a primary purification step: washing the ammonium sulfate primary product A with distilled water, filtering, concentrating, crystallizing and drying the filtrate to obtain an ammonium sulfate intermediate product B.
Still further, the method also comprises a secondary purification step: mixing the ammonium sulfate intermediate product B and water according to the mass ratio of 1:1.5 to obtain a mixed solution C, putting the mixed solution C into a crystallizer, adding sodium sulfate accounting for 0.85% of the mixed solution C by mass, heating to 60 ℃, preserving heat and fully stirring to completely dissolve solids; then adding ammonium sulfate seed crystal which accounts for 5.5 percent of the mass fraction of the mixed solution C, carrying out reduced pressure evaporation at 25 ℃, maintaining the vacuum degree in a crystallizer at 0.08Mpa, stopping reduced pressure evaporation after the evaporated water amount reaches 75 percent of the weight of the added water, carrying out temperature-controlled cooling at the cooling rate of 4 ℃/h, stopping cooling when the temperature is reduced to 9 ℃, carrying out crystal growth for 2.5h, filtering, washing and drying to obtain the finished product of ammonium sulfate.
Example 3
A preparation method of phosphogypsum solid-phase ball milling of ammonium sulfate for water treatment comprises the following steps: weighing a certain amount of phosphogypsum, ammonium bicarbonate and glass balls, adding the glass balls into a ball mill, and starting the ball mill; adding phosphogypsum and ammonium bicarbonate into a ball mill for reaction.
Further, the method also comprises the following steps: and after the reaction is finished, separating the materials from the ball mill, and air-drying the materials to obtain an ammonium sulfate primary product A.
Wherein, the CaSO in the phosphogypsum4·2H2The molar ratio of O to ammonium bicarbonate was 0.58.
And the reaction time is 10-20 min.
And the mass ratio of the total mass of the phosphogypsum and the ammonium bicarbonate to the glass spheres is 1: 4.
And the rotating speed of the ball mill is 700 r/min.
Further, the method also comprises a primary purification step: washing the ammonium sulfate primary product A with distilled water, filtering, concentrating, crystallizing and drying the filtrate to obtain an ammonium sulfate intermediate product B.
Still further, the method also comprises a secondary purification step: mixing the ammonium sulfate intermediate product B and water according to the mass ratio of 1:1.5 to obtain a mixed solution C, putting the mixed solution C into a crystallizer, adding sodium sulfate accounting for 0.85% of the mixed solution C by mass, heating to 60 ℃, preserving heat and fully stirring to completely dissolve solids; then adding ammonium sulfate seed crystal which accounts for 5.5 percent of the mass fraction of the mixed solution C, carrying out reduced pressure evaporation at 25 ℃, maintaining the vacuum degree in a crystallizer at 0.08Mpa, stopping reduced pressure evaporation after the evaporated water amount reaches 75 percent of the weight of the added water, carrying out temperature-controlled cooling at the cooling rate of 4 ℃/h, stopping cooling when the temperature is reduced to 9 ℃, carrying out crystal growth for 2.5h, filtering, washing and drying to obtain the finished product of ammonium sulfate.
Example 4
A preparation method of phosphogypsum solid-phase ball milling of ammonium sulfate for water treatment comprises the following steps: weighing a certain amount of phosphogypsum, ammonium bicarbonate and glass balls, adding the glass balls into a ball mill, and starting the ball mill; adding phosphogypsum and ammonium bicarbonate into a ball mill for reaction.
Further, the method also comprises the following steps: and after the reaction is finished, separating the materials from the ball mill, and air-drying the materials to obtain an ammonium sulfate primary product A.
Wherein, the CaSO in the phosphogypsum4·2H2The molar ratio of O to ammonium bicarbonate was 0.60.
And the reaction time was 10 min.
And the mass ratio of the total mass of the phosphogypsum and the ammonium bicarbonate to the glass spheres is 1: 5.
And the rotating speed of the ball mill is 700 r/min.
Further, the method also comprises a primary purification step: washing the ammonium sulfate primary product A with distilled water, filtering, concentrating, crystallizing and drying the filtrate to obtain an ammonium sulfate intermediate product B.
Still further, the method also comprises a secondary purification step: mixing the ammonium sulfate intermediate product B and water according to the mass ratio of 1:1.5 to obtain a mixed solution C, putting the mixed solution C into a crystallizer, adding sodium sulfate accounting for 0.85% of the mixed solution C by mass, heating to 60 ℃, preserving heat and fully stirring to completely dissolve solids; then adding ammonium sulfate seed crystal which accounts for 5.5 percent of the mass fraction of the mixed solution C, carrying out reduced pressure evaporation at 25 ℃, maintaining the vacuum degree in a crystallizer at 0.08Mpa, stopping reduced pressure evaporation after the evaporated water amount reaches 75 percent of the weight of the added water, carrying out temperature-controlled cooling at the cooling rate of 4 ℃/h, stopping cooling when the temperature is reduced to 9 ℃, carrying out crystal growth for 2.5h, filtering, washing and drying to obtain the finished product of ammonium sulfate.
Comparative example 1
The process of this comparative example differs from that of example 1 only in that the CaSO in the phosphogypsum is4·2H2The molar ratio of O to ammonium bicarbonate was 0.50.
Comparative example 2
The process of this comparative example differs from the process of example 1 only in that, without the primary purification step, the primary product a of ammonium sulfate is directly subjected to a secondary purification step to obtain the finished product ammonium sulfate.
Comparative example 3
The process of this comparative example differs from the process of example 1 only in that the secondary purification step is:
and washing the ammonium sulfate intermediate product B with distilled water, filtering, concentrating, crystallizing and drying the filtrate to obtain the finished product ammonium sulfate.
Test example
The reaction conversion and purity of the finished ammonium sulfate were determined for the methods described in examples 1-4 and comparative examples 1-3.
The free acid (H) in the ammonium sulfate primary product A is determined according to the method in GB/T535-20202SO4) The percentage content of (b) and the nitrogen content in the finished ammonium sulfate; CaSO in phosphogypsum according to chemical formula (I) and each method4·2H2Calculating the molar ratio of O to ammonium bicarbonate to obtain SO in the initial product A of ammonium sulfate after complete reaction4 2-The theoretical percentage content of (A); the calculation formula is as follows:
the purity of the finished product of ammonium sulfate is equal to the nitrogen content in the finished product of ammonium sulfate/21.2 percent multiplied by 100 percent
The results are shown in Table 1.
TABLE 1 EXAMPLES 1-4 AND COMPARATIVE EXAMPLES 1-3 TABLE OF REACTION RESULTS
As can be seen from Table 1, the methods of examples 1-4 have high reaction conversion rate, and the prepared finished ammonium sulfate has high nitrogen content and high purity, and is suitable for water treatment and disinfection of waterworks.
Comparative example 1 CaSO in phosphogypsum at the time of preparation4·2H2The molar ratio of O to ammonium bicarbonate is 0.5, the reactant concentration is low, the reaction rate is slow, and the reaction conversion rate is low. Comparative example 2 a primary purification step was not performed at the time of preparation, and the primary ammonium sulfate product a, which was not subjected to the primary purification step, contained impurities such as calcium carbonate, ammonium gypsum, and a small amount of gypsum in addition to ammonium sulfate, and was substituted into the finished ammonium sulfate in the crystallization of the secondary purification step, resulting in low nitrogen content and low purity of ammonium sulfate in the finished ammonium sulfate. Comparative example 2 in the preparation, the secondary purification step also only adopts distilled water to wash and filter, and then the filtrate is concentrated, crystallized and dried, the method can not completely remove the ammonium gypsum in the ammonium sulfate intermediate product B, and the obtained finished ammonium sulfate still contains impurities, thus leading to low nitrogen content in the finished ammonium sulfate and ammonium sulfateThe purity is low.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that modifications can be made by those skilled in the art without departing from the principle of the present invention, and these modifications should also be construed as the protection scope of the present invention.
Claims (8)
1. A phosphogypsum solid-phase ball-milling preparation method of ammonium sulfate for water treatment is characterized by comprising the following steps: weighing a certain amount of phosphogypsum, ammonium bicarbonate and glass balls, adding the glass balls into a ball mill, and starting the ball mill; adding phosphogypsum and ammonium bicarbonate into a ball mill for reaction.
2. The phosphogypsum solid-phase ball-milling preparation method of ammonium sulfate for water treatment as claimed in claim 1, characterized by further comprising the following steps: and after the reaction is finished, separating the materials from the ball mill, and air-drying the materials to obtain an ammonium sulfate primary product A.
3. The solid-phase ball milling preparation method of phosphogypsum containing ammonium sulfate for water treatment as claimed in claim 1, wherein the molar ratio of CaSO4.2H2O and ammonium bicarbonate in the phosphogypsum is 0.55-0.60.
4. The solid-phase ball milling preparation method of phosphogypsum containing ammonium sulfate for water treatment as claimed in claim 1, wherein the reaction time is 10-20 min.
5. The solid-phase ball milling preparation method of phosphogypsum containing ammonium sulfate for water treatment as claimed in claim 1, wherein the mass ratio of the total mass of phosphogypsum and ammonium bicarbonate to glass spheres is 1: 3-1: 5.
6. The phosphogypsum solid-phase ball-milling preparation method of ammonium sulfate for water treatment as claimed in claim 1, wherein the rotation speed of the ball mill is 600-800 r/min.
7. The solid phase ball milling preparation method of phosphogypsum with ammonium sulfate for water treatment as claimed in claim 2, characterized by further comprising a primary purification step: washing the ammonium sulfate primary product A with distilled water, filtering, concentrating, crystallizing and drying the filtrate to obtain an ammonium sulfate intermediate product B.
8. The phosphogypsum solid-phase ball-milling preparation method of ammonium sulfate for water treatment as claimed in claim 7, characterized by further comprising a secondary purification step: mixing the ammonium sulfate intermediate product B and water according to the mass ratio of 1:1.5 to obtain a mixed solution C, putting the mixed solution C into a crystallizer, adding sodium sulfate accounting for 0.85% of the mixed solution C by mass, heating to 60 ℃, preserving heat and fully stirring to completely dissolve solids; then adding ammonium sulfate seed crystal which accounts for 5.5 percent of the mass fraction of the mixed solution C, carrying out reduced pressure evaporation at 25 ℃, maintaining the vacuum degree in a crystallizer at 0.08Mpa, stopping reduced pressure evaporation after the evaporated water amount reaches 75 percent of the weight of the added water, carrying out temperature-controlled cooling at the cooling rate of 4 ℃/h, stopping cooling when the temperature is reduced to 9 ℃, carrying out crystal growth for 2.5h, filtering, washing and drying to obtain the finished product of ammonium sulfate.
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