CN107188144A - The method that one kind makes MAP and Diammonium phosphate (DAP) with hydrochloric acid decomposing medium and low grade, melamine complex salt crystal legal system - Google Patents
The method that one kind makes MAP and Diammonium phosphate (DAP) with hydrochloric acid decomposing medium and low grade, melamine complex salt crystal legal system Download PDFInfo
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- CN107188144A CN107188144A CN201610145765.3A CN201610145765A CN107188144A CN 107188144 A CN107188144 A CN 107188144A CN 201610145765 A CN201610145765 A CN 201610145765A CN 107188144 A CN107188144 A CN 107188144A
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- ammonium
- hydrochloric acid
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 42
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 19
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title claims abstract description 18
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 title claims description 25
- 229910000388 diammonium phosphate Inorganic materials 0.000 title claims description 20
- 239000005696 Diammonium phosphate Substances 0.000 title claims description 19
- 235000019838 diammonium phosphate Nutrition 0.000 title claims description 19
- 239000013078 crystal Substances 0.000 title claims description 8
- 150000003839 salts Chemical class 0.000 title claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 39
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003337 fertilizer Substances 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 18
- 239000000706 filtrate Substances 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 17
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 14
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 11
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 11
- 239000002367 phosphate rock Substances 0.000 claims abstract description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001110 calcium chloride Substances 0.000 claims abstract description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000000284 extract Substances 0.000 claims abstract description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 7
- 238000005360 mashing Methods 0.000 claims abstract description 7
- 239000012071 phase Substances 0.000 claims abstract description 7
- 239000008346 aqueous phase Substances 0.000 claims abstract description 6
- 238000007664 blowing Methods 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 239000007790 solid phase Substances 0.000 claims abstract description 5
- ZFCRHJMORPMYON-UHFFFAOYSA-G aluminum;magnesium;iron(2+);heptahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Al+3].[Fe+2] ZFCRHJMORPMYON-UHFFFAOYSA-G 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 17
- 229910001510 metal chloride Inorganic materials 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- RNMCQEMQGJHTQF-UHFFFAOYSA-N 3,5,6,7-tetrahydrotetrazolo[1,5-b][1,2,4]triazine Chemical class N1CCN=C2N=NNN21 RNMCQEMQGJHTQF-UHFFFAOYSA-N 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 239000004254 Ammonium phosphate Substances 0.000 claims description 7
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 7
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 5
- 239000006096 absorbing agent Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 229910001051 Magnalium Inorganic materials 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000005191 phase separation Methods 0.000 claims 1
- 230000008929 regeneration Effects 0.000 claims 1
- 238000011069 regeneration method Methods 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 10
- 238000002425 crystallisation Methods 0.000 abstract description 10
- 230000008025 crystallization Effects 0.000 abstract description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000011026 diafiltration Methods 0.000 abstract description 7
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 abstract description 6
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000395 magnesium oxide Substances 0.000 abstract description 5
- 235000019270 ammonium chloride Nutrition 0.000 abstract description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000908 ammonium hydroxide Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 18
- 235000011148 calcium chloride Nutrition 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000012254 magnesium hydroxide Nutrition 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- -1 aluminium phosphoric acid Chemical compound 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004176 ammonification Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 235000019628 coolness Nutrition 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical compound N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/28—Ammonium phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
-
- 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
- C01F11/20—Halides
- C01F11/24—Chlorides
-
- 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
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
-
- 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
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Fertilizers (AREA)
Abstract
A kind of method for manufacturing an ammonium and two ammonium phosphoric acid, it is to decompose any mid low grade phosphate rock with hydrochloric acid, milk of lime is neutralized, decomposed solution and wet solid phase (white fertilizer) must be purified, by the former and melamine reaction generation melamine phosphate crystalline solid and chloride, with ammonium hydroxide and crystallization precursor reactant, ammonium phosphate salt is generated.The melamine discharged is returned and used again, and by upper chloride and crystalline solid wash water and white fertilizer plus hydrochloric acid mashing, HF is driven in heating out of, cooling separates out chloride, add water, plus in milk of lime and produce iron aluminum-magnesium hydroxide and calcium chloride solution, the latter's condensing crystallizing is produced into high-grade calcium chloride.Hydroxide adds dissolving with hydrochloric acid, with N235Extract iron, lead to ammonia and produce ferric ammonium, blowing air is calcined to obtain iron oxide red.Raffinate aqueous phase leads to ammonia and produces magnesium hydroxide, and diafiltration is calcined to be calcined to obtain alumdum without boron magnesia, filtrate and wash water.Gas phase is cooled down, and obtains ammonium chloride.By white residue and calcium chloride in 800 degree Celsius baked above siliceous fertilizer and hydrogen chloride, the latter, which returns, decomposes white fertile.
Description
Technical field：
It is to process phosphorus ore with hydrochloric acid, melamine complex salt crystal legal system makes the technology category of phosphorus ammonium of new generation the invention belongs to the purification of phosphoric acid by wet process ammonium salt and manufacturing technology.
Background technology：
Ammonium phosphate salt is largely used among industry and agricultural production, and annual output reaches millions of tons, and current production method has thermal phosphoric acid and ammonia to neutralize, and slurry-spraying pelletizing produces industry and product, and substantial amounts of or obtained with sulfuric acid wet process phosphoric acid ammonification.It is divided to first to concentrate to neutralize and first neutralize afterwards again in this and concentrates two kinds of flows afterwards, the former is domestic and international classical way, it is required that the relatively good rich ore of phosphorus ore quality, phosphoric acid by wet process and in concentration process due to can constantly separate out iron aluminium phosphoric acid hydrochlorate mud, and must not be without filtering the process concentrated again halfway, when being concentrated to P2O5When >=50% can ammonia neutralize, slurry-spraying pelletizing is domestic because phosphorus ore quality is poor into product, in order to avoid there is intermittent thickening filtration phenomenon, mostly uses elder generation with ammonia and P2O5=30% or so sulfuric acid wet process phosphoric acid, denseer ammonium phosphate solution is concentrated to again removes slurry-spraying pelletizing, this is the distinctive MAP by Ammoniated Slurry Concentrating Process of China, in China's large-scale popularization application, the advantage of this method is can be with the poor phosphorus ore of use quality, concentrator material is solved well, have the disadvantage that product nitrogen and phosphorus content is more lower than classical approach, and iron, aluminium, fluorine, arsenic, lead, the cadmium in phosphorus ore enter in product, these elements can tire out collection in this fertilizer of chronic administration, soil, pollute soil, it is difficult to remove all the life, such crops can also be poisoned.It should administer, i.e., when producing ammonium phosphate product, as far as possible remove these harmful elements from source, because product cost and price inversion phenomenon occur in current China's fertilizer ammonium phosphate enterprises, no energy pays close attention to soil poisoning problem at all.
Domestic University Of Xiangtan has delivered hydrochloric acid method melamine MAP and the report of Diammonium phosphate (DAP)[1]It is that, with activated carbon, soda ash and TBP purify the decomposed solution that hydrochloric acid decomposes poor phosphorus ore.
This technique is changed in milk of lime and decomposed solution removal of impurities, from processing procedure is saltoutd in the acidifying of impurity removing (white fertilizer), reclaims P2O5, reach simplified purification process and high P2O5The purpose of yield.
The content of the invention：
The present invention is to decompose any phosphorus ore using hydrochloric acid, and the method that melamine complex salt crystal legal system makes MAP and two ammoniums is concretely comprised the following steps：
1 decomposes the full mesh phosphorus ore of mistake 40 with hydrochloric acid, and its reaction temperature is 80 degree Celsius or so, and hydrochloric acid consumption is 105% times of the theoretical acid consumption summation of all metal oxides in phosphorus ore, and the reaction time is stirred for 30 minutes to add miberal powder to finish.
2, with industrial filter cloth heat filtering and washing, obtain decomposed solution and white residue.
3 in milk of lime and decomposed solution is to PH=1-3, to filter to get filtrate and wet solid phase (white fertile).
4 by filtrate and melamine in normal-temperature reaction 1 hour, dosage is twice mole of melamine of phosphoric acid molal quantity in filtrate, produces melamine phosphate crystalline solid and metal chloride solutions.
Crystallization of melamine phosphate in 5 filterings, washing.
6 are reacted 30 minutes with Ammonia normal temperature with rear melamine phosphate is washed out, and filtering, washing obtain ammonium phosphate solution and solid phase melamine, and the latter returns to the phosphoric acid that subsequent cycle is gone in the decomposed solution of sediment fraction neutralization.
7 concentrate upper ammonium phosphate solution, crystallize, and dry, produce the MAP and diammonium phosphate product for meeting GB10205-2001 standards.
Upper metal chloride solutions are merged with washing the wash water of melamine phosphate plus hydrochloric acid dissolves with white fertilizer mashing by 8, and heating, which drives hydrogen fluoride out of and returns the absorption of decomposing phosphate rock process fluorine absorber, removes anhydrous hydrogen fluoride processed.
The upper solution of 9 coolings, separates out a large amount of metal chloride crystallizations, separates, elution, crystallization mother liquor and wash water return to decomposing phosphate rock.
The metal chlorides of 10 separation are dissolved in water, and are neutralized with milk of lime and arrive PH=6-7, filtration washing, and filtrate and wash water condensing crystallizing are into high-grade anhydrous calcium chloride (CaCl2=95.8%).
Add dissolving with hydrochloric acid with the metal hydroxides produced in 11, with N235Extractant extracts iron.
12 are passed through gas ammonia in extraction iron organic phase, and the ferric ammonium separating, washing blowing air of generation is calcined and iron oxide red (Fe is obtained2O3=98.2%).
13 are passed through gas ammonia in extraction iron raffinate aqueous phase, produce magnesium hydrate precipitate, diafiltration, roasting and obtain without boron activated magnesia (MgO=95.3%).
The filtrate of 14 filtering magnesium hydroxides and wash water produce alumdum (Al in 150~250 degree of spray pyrolysis Celsius2O3=95.1%).
Pyrolysis gas phase refrigerated separation is obtained ammonium chloride by 15.
16 when calcium chloride dull sale, and by crystallization calcium chloride and white residue mix, half an hour is calcined in 810-820 degree Celsius, obtains siliceous fertilizer and hydrogen chloride, and the latter returns to acidifying and decomposes white fertilizer.
Key reaction formula is：
Ca5F(PO4)3+10HCl-→3H3PO4+5CaCl2+HF
Al2O3+MgO+Fe2O3+14HCl-→2AlCl3+2FeCl3+MgCl2+7H2O
H3PO4+Ca(OH)2-→CaHPO4·2H2O ↓ (white fertilizer)
H3PO4+C3H6N6-→C3H6N6·H3PO4
C3H6N6·H3PO4+NH4OH-→NH4H2PO4+C3H6N6
C3H6N6·H3PO4+2NH4OH-→(NH4)2HPO4+C3H6N6
Brief description of the drawings：
Fig. 1 is the process chart that hydrochloric acid decomposing medium and low grade, melamine complex salt crystal legal system make ammonium phosphate salt.
The full ground phosphate rock for crossing 40 mesh, which is put into, to be heated in 60 degree Celsius of hydrochloric acid, hydrochloric acid dosage is 105% times of the theoretical acid consumption summation of phosphorus ore metal oxide, insulated and stirred 30 minutes again after miberal powder is finished, the fluoro-gas of generation is absorbed with water goes anhydrous HF processed, filter while hot, stacked after white residue washing, sand is can be used as to use, decomposed solution adds milk of lime and neutralized to PH=1-3 while hot, the wet solid phase (white fertilizer) that removal of impurities is produced is pending, in the purification decomposed solution that twice mole of melamine is put into one times of phosphoric acid mole, stirring at normal temperature 1 hour, by the C of generation3H6N6·H3PO4Filtering, C must be cleaned by washing3H6N6·H3PO4And metal chloride solutions, by clean C3H6N6·H3PO4With Ammonia by generation one ammonium and two ammonium ammonification normal-temperature reaction half an hour, ammonium phosphate salt, diafiltration, filtrate and wash water condensing crystallizing are generated, dry ammonium phosphate salt, the C discharged3H6N6Return to subsequent cycle to go to precipitate the phosphoric acid in the decomposed solution purified, by upper metal chloride and generation C3H6N6·H3PO4The filtrate of reaction and wash water merge plus hydrochloric acid dissolves with white fertilizer mashing.The HF driven out of is heated to go in the absorber of phosphorus ore decomposition process to absorb anhydrous HF processed, cool down solution and separate out a large amount of metal chloride crystallizations, suction filtration is eluted, and crystallization mother liquor and wash water return to decomposing phosphate rock, and be dissolved in water this metal chloride, plus milk of lime neutralizes and arrives PH=6-7, iron aluminum-magnesium hydroxide is produced, diafiltration, filtrate and wash water concentration granulation produce high-grade anhydrous calcium chloride, iron aluminum-magnesium hydroxide is added into dissolving with hydrochloric acid, with N235Extractant extraction iron 15 minutes, material temperature 10-45 degree Celsius separates extraction iron organic phase, it is passed through gas ammonia, ferric ammonium is produced, the roasting of ferric ammonium separating, washing blowing air is produced into iron oxide red, extraction iron extractant returns to extraction iron next time, the extraction iron raffinate aqueous phase ventilation ammonia of separation, magnesium hydroxide is settled out, is calcined and is obtained without boron activated magnesia through diafiltration, filtrate is with wash water in 150~250 degree of spray roastings Celsius, alumdum is obtained, gas phase cools down to obtain ammonium chloride.
When calcium chloride dull sale, by crystallization calcium chloride and white residue mix, half an hour is calcined in 810-820 degree Celsius, siliceous fertilizer and hydrogen chloride is obtained, the latter returns to acidifying and decomposes white fertilizer.
Embodiment：
Table 1, raw ore composition
| Title | P2O5 | CaO | MgO | Fe2O3 | Al2O3 | F | Al |
| Weight % | 12.3 | 30.75 | 10.05 | 1.22 | 0.58 | 1.9 | 24.9 |
Claim 1000 grams of full mesh ground phosphate rock of mistake 40, slowly pour into have heated in 60 degree of 1881 milliliters of 30% technical hydrochloric acids Celsius and react, finish again insulated and stirred 30 minutes, fluoro-gas water, which absorbs, goes anhydrous HF processed, heat filtering washs to obtain wet 361 grams of white residue, 2490 grams of filtrate and wash water, with in milk of lime and decomposed solution is to PH=2, suction filtration, 2608 grams of filtrate has 61 grams of phosphatase 11, i.e. 1.64 moles plus 3.28 moles i.e. 422 grams of melamines and 2608 grams of purification decomposed solutions are stirred 1 hour at 28 degree Celsius, filtering eluriates 200 × 1 milliliters of water wash with 300 × 3 milliliters of water, 569 grams of wet melamine phosphate sediment and metal chloride solutions, ammonium hydroxide is added in sediment by one ammonium of generation and two ammonium requirements, adjust pH value, stir half an hour, magma diafiltration, filtrate and wash water concentration, crystallizing and drying, obtain 182 grams of the MAP that purity is 98.2%, purity is 98.3% 216 grams of Diammonium phosphate (DAP), the melamine discharged returns to the phosphoric acid in the decomposed solution that subsequent cycle precipitation has been purified, by upper metal chloride and generation C3H6N6·H3PO4The filtrate of reaction and wash water merge plus hydrochloric acid dissolves with white fertilizer mashing, and HF is driven in heating out of, into the absorber of decomposing phosphate rock process in absorb, go anhydrous HF processed, solution cooling separates out a large amount of metal chloride crystallizations, and magma filtering elution, crystallization mother liquor returns to decomposing phosphate rock with wash water, metal chloride is dissolved in water, neutralized with milk of lime and arrive PH=6-7, diafiltration, filtrate wash water concentration granulates to obtain 1021 grams of anhydrous calcium chloride (purity 95.8%), metal hydroxides adds dissolving with hydrochloric acid, with N235Extractant extract iron, separation extraction iron organic phase, with ammoniacal liquor back extraction generation ferric ammonium, be isolated washing blowing air be calcined 11.2 grams of purity be 98.2% iron oxide red.The extractant that ammoniacal liquor back extraction generation ferric ammonium is isolated returns to the acidifying solution of the metal hydroxides of extraction subsequent cycle, extract raffinate aqueous phase ventilation ammonia during iron, produce magnesium hydroxide and aluminate, magnesium hydroxide is filtered, washing is calcined without 95.2 grams of boron active oxidation magnesium powder (MgO=95.3%), and the solution of filtration washing obtains 5.5 grams of (Al of alumdum in 240~250 degree of spray roastings Celsius2O3=95.1%), the NH of gas phase distillation will be calcined4Solid ammonium chloride is collected to obtain in Cl coolings.By 1021g anhydrous calcium chlorides and the dry white residue mixs of 611g, half an hour is calcined in 810-820 degree Celsius, high activity siliceous fertilizer 1023g and hydrogen chloride 643g is obtained, by hydrogen chloride negative pressure absorbing to white fertilizer mashing retort, decompose white fertilizer.
Table 2, HG/T4511-2013
Bibliography
[1] Chen Fangfei etc. " hydrochloric acid method prepares MAP and Diammonium phosphate (DAP) " Central South University journal (natural science report) in April, 2009 the 2nd phase of volume 40.
Claims (19)
1. one kind is with hydrochloric acid decomposing medium and low grade, melamine complex salt crystal legal system makes second generation phosphorus
The method of a sour ammonium and Diammonium phosphate (DAP)：
With technical hydrochloric acid or hydrogen chloride decomposing phosphate rock, melamine complex salt crystal method manufacture second
For MAP and Diammonium phosphate (DAP).
2. the method described according to claim 1, phosphorus ore used is any grade, any miscellaneous
The how many phosphorus ore of matter content.
3. the method described according to claim 2, with milk of lime and decomposed solution is to PH=1-3,
Filter to obtain decomposed solution and wet solid phase (white fertilizer).
4. the method described according to claim 3, by the decomposed solution purified and melamine
Normal-temperature reaction 1 hour, generates C3H6N6·H3PO4Complex salt crystal body and containing metal chloride solutions.
5. the method described according to claim 4, produced C3H6N6·H3PO4Through overcharging
Washing is divided to be reacted 0.5 hour with Ammonia stirring at normal temperature again.
6. the method described according to claim 5, control mashing material liquid PH value, generates phosphoric acid
One ammonium and Diammonium phosphate (DAP) and melamine are expected admittedly, filtered, are washed, and the melamine of regeneration is returned to
Phosphoric acid in circularly purifying decomposed solution of letting it settle for a while.
7. the method described according to claim 6, by filtrate and wash water condensing crystallizing, drying
Obtain meeting the MAP of GB10205-2001 standards and the product of Diammonium phosphate (DAP).
8. the method described according to claim 4,5, by metal chloride solutions and washing
C3H6N6·H3PO4Wash water merge and drive hydrogen fluoride out of with white fertilizer plus hydrochloric acid mashing heating, containing hydrogen fluoride
Gas returns to the absorption of decomposing phosphate rock process fluorine absorber and removes anhydrous hydrogen fluoride processed.
9. the method described according to claim 8, the solution for driving HF out of is cooled to Celsius
20 degree or so, separate out a large amount of metal chloride crystalline solid.
10. the method described according to claim 9, by magma filtration washing, filtrate and wash water
Return to decomposing phosphate rock.
11. the method described according to claim 9, metal chloride reacts with milk of lime, raw
Into iron aluminum-magnesium hydroxide and calcium chloride, suction filtration, washing, high-grade is made with wash water concentration in filtrate
Anhydrous calcium chloride.
12. the method described according to claim 11, by metal hydroxides plus dissolving with hydrochloric acid,
With N235Extractant extracts iron, and material temperature 10-30 degree Celsius extracts 15 minutes, oil phase: aqueous phase=1: 1.
13. the method described according to claim 12, will extract the organic phase separation of iron, lead to ammonia
Generate ferric ammonium, the extractant of separation return iron in the iron magnalium chloride of extraction subsequent cycle from
Son.
14. the method described according to claim 13, ferric ammonium washing blowing air roasting is given birth to
Into iron oxide red and gas ammonia, gas ammonia returns to front suction ammonia.
15. the method described according to claim 14, leads to ammonia by extraction iron raffinate aqueous phase, separates out
Magnesium hydrate precipitate and aluminate.
16. the method described according to claim 15, magnesium hydroxide is filtered, wash, roasting
Burn and obtain no boron active oxidation magnesium powder.
17. the method described according to claim 16, by aluminate solution Celsius 150~250
Degree thermally decomposes to generate Al2O3, separate to obtain alumdum.
18. the method described according to claim 17, chlorination is collected to obtain by roasting gas phase cooling
Ammonium.
19. the method described according to claim 11, the calcium chloride of separation can be mixed with white residue
Close, be calcined half an hour in 800-1000 degree Celsius, obtain siliceous fertilizer and hydrogen chloride gas, the latter returns to
White fertilizer is decomposed in acidifying.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3880980A (en) * | 1972-11-30 | 1975-04-29 | Allied Chem | Recovery of uranium from HCl digested phosphate rock solution |
| CN1146427A (en) * | 1996-08-23 | 1997-04-02 | 四川绵竹龙蟒矿物质饲料集团有限公司 | Production method for fodder grade calcium hydrogen phosphate |
| CN1308017A (en) * | 2001-02-27 | 2001-08-15 | 天津化工研究设计院 | Impurity screening method for the production process of large-grain feed-level calcium hydrogen phosphate crystal |
| CN101343051A (en) * | 2008-09-02 | 2009-01-14 | 武汉凌派化工科技有限公司 | Method for decomposing phosphorus ore and phosphorus ore containing article with hydrochloric acid to produce phosphoric acid and ammonium phosphate salt |
| CN102992291A (en) * | 2012-12-12 | 2013-03-27 | 贵州开磷（集团）有限责任公司 | Method for preparing feed grade calcium hydrophosphate by phosphorite decomposition by hydrochloric acid |
-
2016
- 2016-03-14 CN CN201610145765.3A patent/CN107188144A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3880980A (en) * | 1972-11-30 | 1975-04-29 | Allied Chem | Recovery of uranium from HCl digested phosphate rock solution |
| CN1146427A (en) * | 1996-08-23 | 1997-04-02 | 四川绵竹龙蟒矿物质饲料集团有限公司 | Production method for fodder grade calcium hydrogen phosphate |
| CN1308017A (en) * | 2001-02-27 | 2001-08-15 | 天津化工研究设计院 | Impurity screening method for the production process of large-grain feed-level calcium hydrogen phosphate crystal |
| CN101343051A (en) * | 2008-09-02 | 2009-01-14 | 武汉凌派化工科技有限公司 | Method for decomposing phosphorus ore and phosphorus ore containing article with hydrochloric acid to produce phosphoric acid and ammonium phosphate salt |
| CN102992291A (en) * | 2012-12-12 | 2013-03-27 | 贵州开磷（集团）有限责任公司 | Method for preparing feed grade calcium hydrophosphate by phosphorite decomposition by hydrochloric acid |
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