CN106220249A - The preparation method of Quadrafos compound fertilizer - Google Patents
The preparation method of Quadrafos compound fertilizer Download PDFInfo
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- CN106220249A CN106220249A CN201610543350.1A CN201610543350A CN106220249A CN 106220249 A CN106220249 A CN 106220249A CN 201610543350 A CN201610543350 A CN 201610543350A CN 106220249 A CN106220249 A CN 106220249A
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 51
- -1 Quadrafos compound Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 34
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011574 phosphorus Substances 0.000 claims abstract description 27
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 27
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 24
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 23
- 239000002002 slurry Substances 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 20
- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 claims abstract description 20
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 15
- 239000000706 filtrate Substances 0.000 claims abstract description 15
- 238000005903 acid hydrolysis reaction Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 12
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 12
- 239000010452 phosphate Substances 0.000 claims abstract description 12
- 230000008014 freezing Effects 0.000 claims abstract description 10
- 238000007710 freezing Methods 0.000 claims abstract description 10
- 238000012216 screening Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 38
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 28
- 239000002367 phosphate rock Substances 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 7
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011435 rock Substances 0.000 claims description 4
- NGLMYMJASOJOJY-UHFFFAOYSA-O azanium;calcium;nitrate Chemical compound [NH4+].[Ca].[O-][N+]([O-])=O NGLMYMJASOJOJY-UHFFFAOYSA-O 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims 2
- 230000003179 granulation Effects 0.000 claims 2
- 238000007654 immersion Methods 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000001704 evaporation Methods 0.000 description 17
- 230000008020 evaporation Effects 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 13
- 229910002651 NO3 Inorganic materials 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 9
- 239000011575 calcium Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000005696 Diammonium phosphate Substances 0.000 description 6
- 235000019838 diammonium phosphate Nutrition 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- 239000006200 vaporizer Substances 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910052586 apatite Inorganic materials 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 229910020027 (NH4)3AlF6 Inorganic materials 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 235000011868 grain product Nutrition 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- 239000002686 phosphate fertilizer Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- DACCGEAJIAWULJ-UHFFFAOYSA-M C(C)C(COP(=O)(OCC(CCCC)CC)[O-])CCCC.[Mg+] Chemical compound C(C)C(COP(=O)(OCC(CCCC)CC)[O-])CCCC.[Mg+] DACCGEAJIAWULJ-UHFFFAOYSA-M 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 2
- 229910052960 marcasite Inorganic materials 0.000 description 2
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000019739 Dicalciumphosphate Nutrition 0.000 description 1
- 206010018910 Haemolysis Diseases 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- NHORPIRSHBGRQJ-UHFFFAOYSA-N [Ca].[Ca].OP(O)(O)=O Chemical compound [Ca].[Ca].OP(O)(O)=O NHORPIRSHBGRQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000184 acid digestion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 description 1
- 229910000390 dicalcium phosphate Inorganic materials 0.000 description 1
- 229940038472 dicalcium phosphate Drugs 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000008588 hemolysis Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- ZOGYOOUMDVKYLM-UHFFFAOYSA-N phosphane phosphorous acid Chemical compound P.OP(O)O ZOGYOOUMDVKYLM-UHFFFAOYSA-N 0.000 description 1
- 229940045916 polymetaphosphate Drugs 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B11/00—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes
- C05B11/04—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid
- C05B11/06—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid using nitric acid (nitrophosphates)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses the preparation method of a kind of Quadrafos compound fertilizer, including: phosphorus ore raw material nitric acid is carried out acidolysis；Filter after acid hydrolysis solution is carried out freezing and crystallizing, it is thus achieved that filtrate；Filtrate is passed through in gas ammonia and obtains and neutralize serosity；It is evaporated neutralization serosity under the conditions of 120～170 DEG C concentrating, it is thus achieved that enriching slurry；By enriching slurry under the conditions of 170～210 DEG C, phosphate radical is made to be polymerized, it is thus achieved that melting charge slurry；Melting charge slurry carries out pelletize, screening prepares Quadrafos complex fertilizer product.Evaporator temperature relative low temperature, polymerization tank high temperature, solve and prepare in Quadrafos nitrophosphate fertilizer product and slip thickness, the problems of line clogging.
Description
Technical field
The present invention relates to phosphate compound fertilizer preparing technical field, particularly relate to one and directly carry out for raw material with phosphorus ore
The preparation method of Quadrafos compound fertilizer.
Background technology
Quadrafos in Quadrafos fertilizer, refers to the general name of poly-orthophosphate and polymetaphosphate, and hydrolyzable is just
Phosphate is absorbed and used by plants, and is often used as phosphate fertilizer.And compare usual orthophosphate phosphate fertilizer, Quadrafos is in fertilizer efficiency
There is many advantages: on the one hand Quadrafos is not directly absorbed by plant in soil, but be progressively hydrolyzed into positive phosphorus
Hydrochlorate is utilized by plant, has good slow-releasing；On the other hand, Quadrafos energy and metallic ions Ca2+、Mg2+、Cu2+、Fe2+
Deng chelating, generate soluble chelating thing, thus promote the crop absorption to metallic element.
At present, prepared by the fertilizer production of Quadrafos, and the most representational is that No. 200780044974.8 patents are adopted
Technical scheme, by apatite raw material nitric acid digestion, recrystallization filters calcium nitrate, finally with ammonia neutralize, evaporation, and steam
Reduce the pressure of evaporation step during Faing, improve the temperature of evaporation step and control the temperature of crystallisation step, make vaporized
In journey, phosphate can be polymerized, thus obtains Quadrafos.
But said method, in actual implementation process, type and quality requirements to phosphorus ore raw material are higher, employing
Apatite is raw material.Phosphorus ore mainly has two big classes: Magmatic Phosphorus lime stone, sedimentary rock type phosphorite.And China's cloud, expensive, river etc.
Region phosphorus ore belongs to sedimentary rock type phosphorite, containing element and organic matters such as abundant magnesium, ferrum, aluminum in phosphorus ore, at neutralization procedure
The dopes such as the substantial amounts of colloid of middle generation, precipitation.In such as N-process, have " R " compound when pH value rises to 2.0
Fe3NH4H8(PO4)6·6H2O generates；When pH is 2.3, " Q " compound (AlFe) NH can be generated4HFPO3·0.5H2O；Work as pH
When being 4.0, have " S " compound FeNH4HF2PO3+AlNH4HF2PO3Generate；AlNH when pH is more than 6.04HF2PO3Can be converted into
(NH4)3AlF6, whole process is " R " to " Q " to " S " to (NH4)3AlF6+SiO2, viscosity all can be caused to steeply rise, cause material
Slurry thickness blocking pipeline, production cannot smooth and easy be carried out.On the other hand, above-mentioned thickness situation based on slurry, at concentration and evaporation
Process can only be carried out in the temperature conditions below 180 degree, the nitrophosphate fertilizer product polyphosphate produced all 5% with
Under, it is thus achieved that fertilizer product in Quadrafos productivity ratio relatively low.Existing domestic majority complex fertilizer product Han Quadrafos mostly is
Quadrafos is individually added as additive form, and cannot be obtained by effective directly preparation method.
Summary of the invention
Present invention is primarily targeted at and a kind of preparation directly carrying out Quadrafos compound fertilizer with phosphorus ore for raw material is provided
Method, it is intended to make phosphate radical be polymerized under condition of normal pressure, promotes the Quadrafos in fertilizer, makes aggregate rate in fertilizer product promote,
And during further prepared by the existing phosphate fertilizer of optimization, slurry thickness blocks pipeline, producing cannot the smooth and easy deficiency carried out.
For achieving the above object, the preparation method of the Quadrafos compound fertilizer that the present invention provides, including:
Phosphorus ore raw material nitric acid is carried out acidolysis, it is thus achieved that acid hydrolysis solution；
By described acid hydrolysis solution deliming, it is thus achieved that filtrate；
Described filtrate gas ammonia is neutralized acquisition and neutralizes serosity；
It is evaporated described neutralization serosity under the conditions of 120～170 DEG C concentrating, it is thus achieved that concentrated pulp；
By described concentrated pulp under the conditions of 170～210 DEG C, phosphate radical is made to be polymerized, it is thus achieved that melting charge slurry；
Described melting charge slurry is carried out pelletize, screening, obtains Quadrafos complex fertilizer product.
Use the said method of the present invention, by separated for the step of evaporation and polymerization, and control respectively vaporizer steams
The temperature sent out is polymerized under the conditions of 170～210 DEG C less than 180 DEG C, in polymerization tank, and polymerization effect is more preferable, and nitrophosphate fertilizer product gathers
Conjunction rate can be stablized 10%～30%, and the highest aggregate rate can reach 40%.Further, evaporator temperature relative low temperature, polymerization are used
The mode of groove high temperature is carried out, and evaporation temperature of reactor does not results in nitrophosphate fertilizer and slip thickness, line clogging less than 175 DEG C
Problems.And being applicable to various types of phosphorus ore raw material such as apatite, phosphorite, raw material is the most available after flotation
In composite heat transfer, it is prepared as the nitrophosphate fertilizer product containing Quadrafos.
Accompanying drawing explanation
Fig. 1 is the flow chart of Quadrafos compound fertilizer of the present invention preparation method.
Detailed description of the invention
The realization of the object of the invention, functional characteristics and advantage will in conjunction with the embodiments, are described further referring to the drawings.Should
Understanding, specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The present invention provides a kind of preparation method directly carrying out Quadrafos compound fertilizer with phosphorus ore for raw material, the preparation of this case
Method comprises the steps:
S10, carries out acidolysis by phosphorus ore raw material nitric acid, it is thus achieved that acid hydrolysis solution；
S20, carries out acid hydrolysis solution freezing and crystallizing, and the four water-calcium nitrate crystal produced in crystallization process is filtered separation,
Obtain filtrate；
S30, is neutralized filtrate gas ammonia, it is thus achieved that neutralize serosity；
S40, is evaporated concentrating by neutralizing serosity, it is thus achieved that concentrated pulp under the temperature conditions of 120～170 DEG C；
S50, makes phosphate radical be polymerized concentrated pulp, it is thus achieved that melting charge slurry under the temperature conditions of 170～210 DEG C；
S60, flow to melting charge slurry comminutor and carries out pelletize, screening, i.e. can get final Quadrafos fertilizer product.
The said method step of the present invention, Integral Thought uses nitric acid solution phosphorus ore raw material, carries out the most respectively crystallizing, mistake
Filter, neutralize, concentrate, polymerization procedure, the most directly prepare Quadrafos complex fertilizer product.Wherein, during concrete steps:
Step S10 uses nitric acid that phosphorus ore raw material is carried out acidolysis digestion, decomposing phosphate rock, makes the insoluble phosphorus in phosphorus ore live
Change, prepare for follow-up product；In this step, main reaction principle equation is:
Ca5F(PO4)3+10HNO3→5Ca(NO3)2+3H3PO4+HF↑；
Simultaneously as except main constituent in the sedimentary rock type phosphorite phosphorus ore raw material of the area such as China's cloud, expensive, river main product
Ca5F(PO4)3Outside, possibly together with MgO, Fe2O3、Al2O3、FeS2, Organic substance and carbonate etc., therefore in this nitric acid solution process
In be accompanied by the side reaction that comparison is many, concrete reaction equation has:
MgO+2HNO3→Mg(NO3)2+H2O
Fe2O3+6HNO3→2Fe(NO3)3+3H2O
Al2O3+6HNO3→2Al(NO3)3+3H2O
FeS2+HNO3→Fe(NO3)3+NOx↑+SO2↑+H2O
CaCO3+2HNO3→Ca(NO3)2+H2O+CO2↑
CaCO3+MgCO3+4HNO3→Ca(NO3)2+Mg(NO3)2+2H2O+2CO2↑；
Therefore, in the acidolysis product slurry generated, HNO is mainly contained3、H3PO4、Ca(NO3)2, acid non-soluble substance and H2O etc.；
If the nitric acid amount added in acidolysis is the most not enough, then there is following reaction:
Ca5F(PO4)3+14HNO3→3Ca(H2PO4)2+7Ca(NO3)2+2HF↑；
In order to ensure that phosphorus ore can sufficiently be extracted in this step S10, the consumption generally using nitric acid can be the most sufficient
Measuring, nitric acid uses mass fraction 50～the nitric acid of 65%.
After the acidolysis of step S10, the part acid non-soluble substance in acid hemolysis process is removed, obtain the mixed of liquid phase and insoluble solid phase
Close serosity；The most further the mixed serum of this acidolysis is transferred among cryoprobe in step S20, carry out freezing knot
Brilliant process, the purpose of freezing and crystallizing is that the calcium ion in serosity is changed into Ca (NO3)2·4H2The crystal form of O separates out.Ca
(NO3)2·4H2The fusing point of O is between 40～45 DEG C, and when temperature is less than this temperature range, calcium nitrate can change into crystal
Form separates out and is suspended in serosity.For ensureing crystalline rate, the temperature of freezing and crystallizing controls to enter under the conditions of-10～10 DEG C
OK.By double drum filter after crystallization, the thick calcium nitrate (Ca (NO of crystallization that double drum filter is filtered3)2·
4H2O crystal and part acid non-soluble substance) deliver to calcium ammonium nitrate workshop through filtering, neutralize, evaporate, concentrating, pelletize, screening, prepare complete
Water-soluble calcium ammonium nitrate fertilizer product.Liquid phase after filtering in double drum filter is the filtration containing titanium pigment acid group
Liquid, carries out the preparation of the Quadrafos compound fertilizer of this case in following step.
The filtrate gas ammonia that step S20 is obtained by step S30 further is neutralized, after being filtered by calcium nitrate with gas ammonia
Filtrate neutralize, make filtrate by highly acid H3PO4And HNO3Become weakly acidic ammonium salt slip, its reaction side neutralized
Formula is:
NH3+HNO3→NH4NO3
NH3+H3PO4→NH4H2PO4
NH4H2PO4+NH3→(NH4)2HPO4；
It is the primary response of N-process in above-mentioned reaction, on the basis of primary response, the most also can be along with the phosphorus generated
Acid one ammonium and the Ca (NO in filtrate3)2With Mg (NO3)2A series of side reaction occurs, and reaction equation is as follows:
NH4H2PO4+Ca(NO3)2→Ca(H2PO4)2+2NH4NO3
2NH4H2PO4+Mg(NO3)2→Mg(H2PO4)2+2NH4NO3
Now, carrying out continuing to neutralize if continuing to be passed through gas ammonia, one-lime phosphate and phosphoric acid one magnesium can be converted into again phosphoric acid
Dicalcium and di(2-ethylhexyl)phosphate magnesium, reaction equation is:
Ca(H2PO4)2+Ca(NO3)2+2NH3→CaHPO4+2NH4NO3
Mg(H2PO4)2+Mg(NO3)2+2NH3→MgHPO4+2NH4NO3；
Continuing to neutralize, dicalcium phosphate and di(2-ethylhexyl)phosphate magnesium change into again DFP and three magnesium, and reaction equation is:
2CaHPO4+Ca(NO3)2+2NH3→Ca3(PO4)2+2NH4NO3
2MgHPO4+Ca(NO3)2+2NH3→Mg3(PO4)2+2NH4NO3；
More than for the dominant response process that can occur in gas ammonia N-process, but containing abundant in phosphorus ore raw material
During the elements such as magnesium, ferrum, aluminum, containing Mg in the filtrate that step S20 obtains2+、Fe3+And Al3+Deng impurity, can be formed when neutralizing
Complicated compound they be gelatinous fine crystalline body, whole during compound be changed into " R " to " Q " in detail extremely
" S " is to (NH4)3AlF6+SiO2(seeing the description of background section), thus results in phosphoric acid and increases；Especially at pH=
When about 2.7, viscosity peaks, and occurs again another viscosity peak district subsequently when about pH=4, can make neutralization operation
Cannot smooth and easy carry out；Therefore the gas ammonia N-process of this step S30 should avoid high viscosity district when operating.
In N-process, in addition to slip pH has considerable influence to viscosity, in phosphorus ore, neutralization viscosity plays also by content of MgO
Critical impact, especially when content of MgO is more than 1.5%, then can make to occur frequently existing Severe blockage phenomenon neutralizing time-frequency.
In N-process, when slip neutralize pH be more than 4.3 time, neutralize and do the trick, but due to this
Time MAP crystallization temperature higher, exceed neutralize reaction slurry temperature, the most easily occur MAP needle-like knot
Crystalline substance, is greatly increased the viscosity of slip.When slip exists part Diammonium phosphate (DAP), the crystallization temperature of MAP can be reduced,
Need to continue neutralization for this makes slip pH value improve to 4.8～5.0 to make part MAP be transformed into Diammonium phosphate (DAP) from 4.3,
Reaction equation is:
NH4H2PO4+NH3→(NH4)2HPO4；
When the content of diammonium reaches the 20% of ammonium phosphate total amount, the crystallization temperature of MAP is minimum.
Neutralizing reaction is a strong exothermic reaction, and its reaction can make slurry temperature raise, its reaction heat is about 1.3 ×
104Kcal/100kg mother solution, owing to the crystallization temperature of MAP is higher, therefore to ensure phosphoric acid in N-process
One crystalline ammonium and cause the phenomenon of slip thickness, neutral temperature typically must require to protect higher than the crystallization temperature of MAP
Card neutral temperature is 125～135 DEG C.Increase the N/P of slip simultaneously2O5Produce part Diammonium phosphate (DAP) with controlling to neutralize, reduce slip
Concentration, improves water content etc. and can avoid neutralizing the thickness of slip.
After gas ammonia neutralizes, step S30 makes mother solution by highly acid H3PO4And HNO3Become weakly acidic ammonium salt slip
After, in order to the requirement making the product component in slurry can be suitable in final production Quadrafos compound fertilizer for N/P ratio is (logical
Often N/P ratio >=0.95 of fertilizer nutrient product), after gas ammonia has neutralized, step S30 also needs to obtain after neutralizing
Neutralization slurry in add ammonium nitrate, adjust the N/P of slip2O5。
The neutralization serosity of acquisition is transferred in vaporizer carry out heating evaporation concentration by step S40 further, removes a large amount of
Moisture, to meet the requirement of pelletize.The process of evaporation and concentration needs to be monitored at any time, and the process of evaporation is carried out to concentration of slurry
After reaching more than 97% (i.e. water content controls within 3%), obtain concentrated pulp.
After evaporation and concentration, the concentrated pulp that previous step obtains is transferred in polymerization tank carry out phosphate radical by step S50
Polymerization, concrete operations for being continuously heating to 170～210 DEG C, then orthophosphoric acid ion (PO4) occur polymerization to generate pyrophosphate
(P2O7 2-), tripolyphosphate (P3O10) etc. or Me (PO3) (wherein, Me is NH to n4, the monovalention such as potassium).The time of polyreaction
In the range of being preferably controlled in 1.0～3.0 hours.
After polymerization procedure, final step S60 the melting charge slurry that polymerization procedure obtains is flow to comminutor carry out pelletize,
Screenings etc. process, thus obtain the nitrophosphate fertilizer grain products of 1～4mm.Meanwhile, in this step based on different composite fertilizer class
Type, can also add different compound feed compositions before pelletizing.Such as, if the final products produced are containing potassium, trace
The complex fertilizer product of element, then during pelletize, can supplement interpolation potash fertilizer and trace element in melting charge slurry；That
Obtain after pelletize, screening is containing potassium, the compound fertilizer granules of trace element.
Use the said method of the present invention, although in the step of evaporation and concentration and polymerization, all have polyreaction occur,
But by separated for the step of evaporation and polymerization, and control in vaporizer the temperature of evaporation respectively less than 175 DEG C, in polymerization tank
Being polymerized under the conditions of 170～210 DEG C, polymerization effect is more preferable, and nitrophosphate fertilizer product aggregate rate can be stablized 10%～30%, the highest
Aggregate rate can reach 40%.And, use evaporator temperature relative low temperature, the mode of polymerization tank high temperature to carry out, evaporate reactor
Temperature does not results in nitrophosphate fertilizer and slip thickness less than 175 DEG C, does not results in evaporation and goes the problems of line clogging.And
And it being applicable to the phosphorus ore raw material of the various quality such as apatite, phosphorite and type, raw material directly just can be used for being combined after flotation
Fertile production, is prepared as the nitrophosphate fertilizer product containing Quadrafos.
For making the details of said method process of the present invention be more conducive to understanding and the enforcement of those skilled in the art and prominent
The progressive effect of the phosphate height polymerization yield rate that this case method directly prepares, comes this below by way of specific embodiment
The said method of case is illustrated.
Embodiment 1
In the present embodiment 1, use the type of production ground phosphate rock of the domestic middle alliance phosphorus industry bought as raw material, use this case
Method carry out production and the preparation of Quadrafos compound fertilizer, carrying out with reference to following steps of preparation:
S10, approximately according to the effective ingredient (P in ground phosphate rock2O5About 32%, CaO about 48%, MgO about 1.5%, acid insoluble
Thing 9%, Fe2O3And Al2O3A total of about 3%, moisture and other account for 6.5%), the most first calculate the consumption of required nitric acid be nitric acid/
Ground phosphate rock is stoichiometry 1.1: 1, and wherein nitric acid uses commercially available 58%HNO3。
Then, in acidolysis groove, ground phosphate rock is acidified by the ground phosphate rock raw material nitric acid of above-mentioned 58% concentration, nitric acid
Addition than estimator little over amount, and acidifying during stir, the time of acidifying can be the longest so that it is has reacted
Entirely；
After acidolysis completes, by acid non-soluble substance through precipitate and separate out, the acid hydrolysis solution after acid non-soluble substance will then have been separated
For following step S20.
S20, is transferred to the acid hydrolysis solution of step S10 in freezing and crystallizing device carry out freezing, and sets freezing and crystallizing device
Temperature is-5 DEG C；At the beginning of crystallization, a small amount of Ca (NO can be spread in acid hydrolysis solution3)2·4H2The mother that the crystalline flour of O generates as crystal
Core；Then standing a period of time is after calcium nitrate separates out completely from acid hydrolysis solution, filters and carries out solid-liquid separation, collects filtrate and is used for
Subsequent step.
S30, the filtrate that step S20 is collected, it is transferred to neutralize in reactive tank and be passed through gas ammonia wherein, makes mother solution by by force
Acid H3PO4And HNO3Become weakly acidic ammonium salt slip, and add the N/P of ammonium nitrate adjustment slip2O5, and be passed through at gas ammonia
During, the serosity in stirred tank, and monitor pH value in real time, it is to avoid generate at the viscous compound such as " R ", " Q ", " S "
During high viscosity pH value, (2.7,4.0) keep for a long time；After the pH being neutralized to serosity reaches 5.3～6.0, can stop being passed through gas
Ammonia, the neutralization serosity being sufficiently stirred for obtaining afterwards continues on for subsequent step.
S40, is transferred to the neutralization serosity that step S30 obtains in vaporizer be evaporated concentrating, controls in evaporation process
The temperature of vaporizer is 140 DEG C, during until being concentrated into more than 97%, stopping evaporation, and the concentrated pulp of acquisition is used for follow-up step
Suddenly.
S50, the slip after step S40 being concentrated causes polymerization reaction trough, carries out phosphate radical under the temperature conditions of 200 degree
Polyreaction, in this step, the time of polyreaction can somewhat control longer, keeps melted 2.5 hours；
S60, the melting charge slurry obtained after step S50 polymerization reaction trough is polymerized, it flow to comminutor and carry out pelletize, and making
Sieve after Li, obtain the nitrophosphate fertilizer grain products of final 1～4mm standard specifications.
In order to verify whether the aggregate rate containing Quadrafos in final granulated fertilizer has more satisfactory, by standard weights
(10g) nitrophosphate fertilizer grain products send test in laboratory analysis, water-soluble phosphorus 10.74%, orthophosphate 7.8%, aggregate rate
26.28%, moisture 1.22%.
The fertilizer component analysis result prepared from the examples detailed above of this case, the most existing direct preparation method can only when implementing
Temperature conditions below 180 degree is prepared, it is thus achieved that phosphatic aggregate rate the most high.And preparing
Cheng Zhong, slip viscosity, mobility in each reactor is relatively mild, does not especially have viscous grumeleuse on vaporizer wall
Situation occurs, compares existing method evaporation and polymerization completed in the lump, and the process of production is more smooth and easy.
These are only the preferred embodiments of the present invention, not thereby limit the scope of the claims of the present invention, every utilize this
Equivalent structure or equivalence flow process that bright description and accompanying drawing content are made convert, or are directly or indirectly used in other relevant skills
Art field, is the most in like manner included in the scope of patent protection of the present invention.
Claims (7)
1. the preparation method of a Quadrafos compound fertilizer, it is characterised in that including:
Phosphorus ore raw material nitric acid is carried out acidolysis, it is thus achieved that acid hydrolysis solution；
By described acid hydrolysis solution deliming, it is thus achieved that filtrate；
Described filtrate gas ammonia is neutralized acquisition and neutralizes serosity；
It is evaporated described neutralization serosity under the conditions of 120～170 DEG C concentrating, it is thus achieved that concentrated pulp；
By described concentrated pulp under the conditions of 170～210 DEG C, phosphate radical is made to be polymerized, it is thus achieved that melting charge slurry；
Described melting charge slurry is carried out pelletize, screening, obtains Quadrafos complex fertilizer product.
2. the preparation method of Quadrafos compound fertilizer as claimed in claim 1, described phosphorus ore raw material includes Magmatic Phosphorus ash
At least one in stone, sedimentary rock type phosphorite.
3. the preparation method of Quadrafos compound fertilizer as claimed in claim 1, it is characterised in that by described acid hydrolysis solution deliming
For:
Described acid hydrolysis solution is carried out freezing and crystallizing in-10～10 DEG C and separates four water-calcium nitrate crystal.
4. the preparation method of Quadrafos compound fertilizer as claimed in claim 1, it is characterised in that described melting charge slurry is carried out
In pelletize, screening step, pelletize mode includes biaxial granulation, high-tower granulation, oil immersion pelletize, drum granulating.
5. the preparation method of Quadrafos compound fertilizer as claimed in claim 1 or 2, it is characterised in that by described neutralization serosity
It is evaporated concentrating under the conditions of 120～170 DEG C, it is thus achieved that in the step of concentrated pulp, the concentration of described concentrated pulp is more than 97%.
6. the preparation method of Quadrafos compound fertilizer as claimed in claim 1 or 2, it is characterised in that by described concentrated pulp in
Carrying out under the conditions of 170～210 DEG C in polymerization procedure, the time of polyreaction is 1.0～3.0 hours, and polyreaction is in normal pressure
Under the conditions of carry out.
7. the preparation method of Quadrafos compound fertilizer as claimed in claim 2, it is characterised in that by described acid hydrolysis solution in-10
～after 10 DEG C carry out freezing and crystallizing and separate four water-calcium nitrate crystal step, after the four water-calcium nitrate separating acquisition is melted,
Through filtering, neutralize, evaporate, concentrating, pelletize, screening, make the most water-soluble calcium ammonium nitrate fertilizer product.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108101586A (en) * | 2017-12-13 | 2018-06-01 | 贵州芭田生态工程有限公司 | A kind of nitric acid solution phosphorus ore freezing decalcification mother liquor prepares Nitro Phosphate Unit and method |
| CN109399688A (en) * | 2018-10-17 | 2019-03-01 | 贵州芭田生态工程有限公司 | The method of phosphate fertilizer mother liquor low temperature decalcification and decalcification filtrate and phosphate fertilizer preparation method |
| CN109422549A (en) * | 2017-08-29 | 2019-03-05 | 贵州芭田生态工程有限公司 | Calcium ammonium nitrate particle preparation system and preparation method |
| CN110734304A (en) * | 2018-07-19 | 2020-01-31 | 贵州芭田生态工程有限公司 | Nitrophosphate fertilizer and preparation method thereof |
| CN112939682A (en) * | 2021-02-22 | 2021-06-11 | 深圳市芭田生态工程股份有限公司 | Preparation method of polyphosphate synergistic nitrophosphate fertilizer |
| CN115321504A (en) * | 2022-08-22 | 2022-11-11 | 杨立国 | Full-water-soluble polymer and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1651488A (en) * | 2004-12-23 | 2005-08-10 | 云南省化工研究院 | Production method of poly ammonium phosphate |
| CN1935747A (en) * | 2005-09-22 | 2007-03-28 | 郑州大学 | Method for preparing clean urea-sulfuricacid compound-mixed fertilizer |
| CN101595078A (en) * | 2006-12-05 | 2009-12-02 | 亚拉国际有限公司 | Process for the preparation of NPK or NP materials comprising polyphosphates |
| CN104909841A (en) * | 2015-05-06 | 2015-09-16 | 贵州省化工研究院 | Process for preparing calcium magnesium ammonium phosphate and calcium magnesium ammonium nitrate through nitric acid decomposition of low-medium graded phosphate ore |
-
2016
- 2016-07-12 CN CN201610543350.1A patent/CN106220249A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1651488A (en) * | 2004-12-23 | 2005-08-10 | 云南省化工研究院 | Production method of poly ammonium phosphate |
| CN1935747A (en) * | 2005-09-22 | 2007-03-28 | 郑州大学 | Method for preparing clean urea-sulfuricacid compound-mixed fertilizer |
| CN101595078A (en) * | 2006-12-05 | 2009-12-02 | 亚拉国际有限公司 | Process for the preparation of NPK or NP materials comprising polyphosphates |
| CN104909841A (en) * | 2015-05-06 | 2015-09-16 | 贵州省化工研究院 | Process for preparing calcium magnesium ammonium phosphate and calcium magnesium ammonium nitrate through nitric acid decomposition of low-medium graded phosphate ore |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109422549A (en) * | 2017-08-29 | 2019-03-05 | 贵州芭田生态工程有限公司 | Calcium ammonium nitrate particle preparation system and preparation method |
| CN108101586A (en) * | 2017-12-13 | 2018-06-01 | 贵州芭田生态工程有限公司 | A kind of nitric acid solution phosphorus ore freezing decalcification mother liquor prepares Nitro Phosphate Unit and method |
| CN110734304A (en) * | 2018-07-19 | 2020-01-31 | 贵州芭田生态工程有限公司 | Nitrophosphate fertilizer and preparation method thereof |
| CN109399688A (en) * | 2018-10-17 | 2019-03-01 | 贵州芭田生态工程有限公司 | The method of phosphate fertilizer mother liquor low temperature decalcification and decalcification filtrate and phosphate fertilizer preparation method |
| CN112939682A (en) * | 2021-02-22 | 2021-06-11 | 深圳市芭田生态工程股份有限公司 | Preparation method of polyphosphate synergistic nitrophosphate fertilizer |
| CN115321504A (en) * | 2022-08-22 | 2022-11-11 | 杨立国 | Full-water-soluble polymer and preparation method and application thereof |
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