CN107792840A - A kind of method that accessory substance ferrophosphorus using industrial yellow phosphorus production prepares ferric phosphate - Google Patents
A kind of method that accessory substance ferrophosphorus using industrial yellow phosphorus production prepares ferric phosphate Download PDFInfo
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- CN107792840A CN107792840A CN201711018339.4A CN201711018339A CN107792840A CN 107792840 A CN107792840 A CN 107792840A CN 201711018339 A CN201711018339 A CN 201711018339A CN 107792840 A CN107792840 A CN 107792840A
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- Prior art keywords
- ferrophosphorus
- solution
- solid sediment
- ferric phosphate
- isolated
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 23
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 23
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 21
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000000126 substance Substances 0.000 title claims abstract description 20
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 63
- 239000013049 sediment Substances 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 32
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000000047 product Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011780 sodium chloride Substances 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 14
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 16
- 239000012452 mother liquor Substances 0.000 claims description 14
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910052793 cadmium Inorganic materials 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- 229910052785 arsenic Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910052745 lead Inorganic materials 0.000 claims description 6
- 229910052753 mercury Inorganic materials 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 238000004513 sizing Methods 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052742 iron Inorganic materials 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000002386 leaching Methods 0.000 abstract 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000012047 saturated solution Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- -1 Iron phosphate compound Chemical class 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010563 solid-state fermentation Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 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
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
Abstract
The invention discloses a kind of method that accessory substance ferrophosphorus using industrial yellow phosphorus production prepares ferric phosphate, belong to industrial by-products and utilize field.The present invention uses potassium chlorate acid solution Oxidation Leaching ferrophosphorus, obtain iron content, the aqueous solution of phosphate radical, the purified abjection impurity element of the aqueous solution, the aqueous slkali of leaching separation adjust pH to neutrality, isolated solid sediment, solid sediment is sized mixing with water and demodulates pH to 1 ~ 2 with phosphoric acid solution, isolated solid sediment, scrubbed, dry and calcining obtain ferric phosphate；The solution that precipitation and separation obtains is through being concentrated by evaporation, crystallisation by cooling, isolated sodium chloride product.The inventive method process equipment is simple, and operation is easy, safety, using chemical products of the trade waste production with high added value and wider application, realizes utilization of resources, can reach recycling economy, energy-saving and emission-reduction purpose.
Description
Technical field
The present invention relates to a kind of method that accessory substance ferrophosphorus using industrial yellow phosphorus production prepares ferric phosphate, belongs to industrial secondary
Product utilization field.
Background technology
Ferrophosphorus is caused accessory substance in industrial yellow phosphorus production process, industrially often produces 1t yellow phosphorus, can by-product ferrophosphorus
0.1-0.2 t, estimated by current domestic industry yellow phosphorus annual production, domestic annual about 100,000 tons of yellow phosphorus industry by-product ferrophosphorus.Ferrophosphorus
Main component be phosphorus and iron, carbon, sulphur simultaneously containing a small amount of silicon, calcium, manganese and residual etc., wherein ferrophosphorus content reaches 80-
95%。
At present, utilization of the most domestic phosphorous chemical industry manufacturing enterprise to by-product ferrophosphorus is still insufficient, and some enterprises directly will
It, so as to cause the ferrophosphorus utilization of resources in phosphorous chemical industry low in economic efficiency, in a disguised form causes ferrophosphorus resource as Solid state fermentation
Significant wastage, and environment is damaged.
Ferric phosphate also known as high ferric phosphate, ferric orthophosphate, molecular formula FePO4, the color of the phosphate dihydrate iron of high-purity is
Near-white is shallow（It is light）Yellow-white powder, with the loss of the crystallization water, color gradually turns yellow, and pure anhydride is in yellow-white powder.
Iron phosphate compound has good application in fields such as agricultural, glass-ceramic, steel and surface passivations.Because its unique catalysis is special
Property, ion-exchange capacity and chemical property, have more and more important application in the field such as catalysis and electrode material of lithium battery.
Important component of the positive electrode as lithium ion battery, chemical property, the safety of battery are decide to a certain extent
Property and manufacturing cost etc., and ferric phosphate is one of presoma of synthesizing iron lithium phosphate, it is closely similar with the structure of LiFePO4,
As long as controlling structure, pattern and the granule size of ferric phosphate, the performance of LiFePO4 just can be preferably controlled.
The content of the invention
For ferrophosphorus recycling problem in the prior art, the present invention provides a kind of by-product produced using industrial yellow phosphorus
The method that thing ferrophosphorus prepares ferric phosphate, valuable element phosphorus and iron in ferrophosphorus are extracted, preparing has high added value and relatively wide application
The ferric phosphate of scope, secondary resource recycling is can reach, realizes recycling economy, energy-saving and emission-reduction purpose, be ferrophosphorus accessory substance
Utilization provide an effective approach, improve its application value.
A kind of method that accessory substance ferrophosphorus using industrial yellow phosphorus production prepares ferric phosphate, is comprised the following steps that：
（1）Mixed solution A is prepared in the reactor, is then added and is ground to material all by the ferrophosphorus of 200 mesh sieves, normal
Leach reaction 6 ~ 8h, isolated leachate B under conditions of pressure, temperature are 80 ~ 95 DEG C, mixing speed is 300 ~ 500rpm；Its
Middle mixed solution A is the mixed aqueous solution of potassium chlorate and hydrochloric acid；
（2）According to the total mole number and S of Pb, Cd, Hg, As, Cu metal ion in solution2-The ratio of ion is 1:(1~
1.2) ratio, under conditions of normal pressure, room temperature, mixing speed are 300 ~ 500rpm, in step（1）Add in gained leachate B
Enter sulfide and react the isolated solid sediment C and purifying filter liquor D of 0.5~2.0h；
（3）Under conditions of normal pressure, room temperature, mixing speed are 300 ~ 500rpm, in step（2）Added in gained purifying filter liquor D
Sodium hydroxide solution, regulation pH value of solution continue 0.5 ~ 1.0h of reaction isolated solid sediment E and filtrate F, filtrate F to 4 ~ 6
It is evaporated concentration, crystallisation by cooling, isolated sodium chloride product and mother liquor I, mother liquor I return to step（1）Prepare mixed solution
A；
（4）Add water in reactor, under conditions of normal pressure, room temperature, mixing speed are 300 ~ 500rpm, add step
（3）Gained solid sediment E, phosphoric acid is slow added into after sizing mixing uniformly and adjusts pH value of solution to 1 ~ 2 and reacts 0.5 ~ 1.0h separation
Solid sediment G and filtrate H are obtained, solid sediment G obtains solid sediment I and cleaning solution J, solid through water washing to neutrality
Processing is dried in sediment I, is subsequently placed under the conditions of temperature is 500 ~ 700 DEG C and is calcined 1 ~ 2h, cools down and produce phosphoric acid iron product；
（5）By step（4）Gained filtrate H and cleaning solution J is well mixed return to step（4）Middle substitution water is added in reactor；
The step（1）The mass concentration of potassium chlorate is 30 ~ 40% in mixed solution A, and the mass concentration of hydrochloric acid is 3 ~ 6%, mixing
The solid mass ratio of the liquid of solution A and ferrophosphorus is (12 ~ 16):1；
The step（2）The sulfide added in leachate B is vulcanized sodium, phosphorus pentasulfide or hydrogen sulfide；
The step（4）Reclaimed water and the solid sediment E solid mass ratio of liquid are (4 ~ 6):1；
The industrial by-products of output, its main component are usual when the ferrophosphorus is industrially produces industrial yellow phosphorus using electric furnace process
For：P 18 ~ 30%, Fe 50 ~ 75%, Si 0.1 ~ 3.0%, Ca 0.05 ~ 1.0%, Mn 0.2 ~ 2.0%, additionally containing Pb, Cd,
The material such as the precious metals such as Cr, Ni, V, Co, Ti and the carbon of residual, sulphur；
Beneficial effects of the present invention：
（1）Method utilizes P, Fe valuable element contained in ferrophosphorus, leaches the iron and phosphorus in ferrophosphorus, production tool by acidic oxidation
There is the ferric phosphate of high added value and wider application；
（2）The inventive method process equipment is simple, and operation is easy, safety, realizes the recycling of ferrophosphorus secondary resource, and realization follows
Ring economy, energy-saving and emission-reduction purpose.
Embodiment
The present invention is described in further detail with reference to embodiment, but protection scope of the present invention and unlimited
In the content.
Embodiment 1：A kind of method that accessory substance ferrophosphorus using industrial yellow phosphorus production prepares ferric phosphate, specific steps are such as
Under：
（1）Mixed solution A is prepared in the reactor（Mixed solution A is the mixed aqueous solution of potassium chlorate and hydrochloric acid）, then add again
Enter to be ground to material all by the ferrophosphorus of 200 mesh sieves, under conditions of normal pressure, temperature are 90 DEG C, mixing speed is 300rpm
Leach reaction 6h, isolated leachate B；The mass concentration of potassium chlorate is 40% wherein in mixed solution A, and the quality of hydrochloric acid is dense
Spend for 6%, the solid mass ratio of liquid of mixed solution A and ferrophosphorus is 12:1；
（2）Under conditions of normal pressure, room temperature, mixing speed are 300rpm, in step（1）Sulfide is added in gained leachate B
（Sulfide is phosphorus pentasulfide）And react 1.5h isolated solid sediment C and purifying filter liquor D；Pb in wherein leachate B,
The total mole number and sulfide of Cd, Hg, As, Cu metal ion（Phosphorus pentasulfide）Middle S2-The ratio of the molal quantity of ion is 1:1；
（3）Under conditions of normal pressure, room temperature, mixing speed are 300rpm, in step（2）Quality is added in gained purifying filter liquor D
The sodium hydroxide solution of concentration 20%, regulation pH value of solution to 5, continue to react the isolated solid sediment E and filtrate F of 1.0h, filter
Liquid F is evaporated concentration, crystallisation by cooling, isolated sodium chloride product and mother liquor I, mother liquor I return to step（1）It is molten to prepare mixing
Liquid A；NaCl mass percents content is 98.73% in the present embodiment sodium chloride product；
（4）According to the solid mass ratio 5 of water and solid sediment E liquid:1 ratio, is added water in reactor, in normal pressure, room
Under conditions of temperature, mixing speed are 300rpm, step is added（3）Gained solid sediment E, it is slow added into after sizing mixing uniformly
The phosphoric acid that mass concentration is 85% adjusts pH value of solution and to 1 and reacts 0.5h isolated solid sediment G and filtrate H, solid precipitation
Thing G obtains solid sediment I and cleaning solution J through water washing to neutrality, and solid sediment I is placed under the conditions of temperature is 140 DEG C and done
Dry 5h, it is subsequently placed under the conditions of temperature is 600 DEG C and is calcined 1h, cool down and produce phosphoric acid iron product；
After testing, Fe contents are 36.25% in phosphoric acid iron product in the present embodiment, P content 20.17%, and Fe and P mol ratio are
1:1.00, outward appearance is white.
Embodiment 2：A kind of method that accessory substance ferrophosphorus using industrial yellow phosphorus production prepares ferric phosphate, specific steps are such as
Under：
（1）Mixed solution A is prepared in the reactor（Mixed solution A is the mixed aqueous solution of potassium chlorate and hydrochloric acid）, then add again
Enter to be ground to material all by the ferrophosphorus of 200 mesh sieves, under conditions of normal pressure, temperature are 80 DEG C, mixing speed is 500rpm
Leach reaction 8h, isolated leachate B；The mass concentration of potassium chlorate is 30% wherein in mixed solution A, and the quality of hydrochloric acid is dense
Spend for 3%, the solid mass ratio of liquid of mixed solution A and ferrophosphorus is 16:1；
（2）Under conditions of normal pressure, room temperature, mixing speed are 500rpm, in step（1）Sulfide is added in gained leachate B
（Sulfide is vulcanized sodium）And react 0.5h isolated solid sediment C and purifying filter liquor D；Pb, Cd in wherein leachate B,
The total mole number and sulfide of Hg, As, Cu metal ion（Vulcanized sodium）Middle S2-The ratio of the molal quantity of ion is 1:1.2；
（3）Under conditions of normal pressure, room temperature, mixing speed are 500rpm, in step（2）Quality is added in gained purifying filter liquor D
The sodium hydroxide solution of concentration 10%, regulation pH value of solution to 6, continue to react the isolated solid sediment E and filtrate F of 0.5h, filter
Liquid F is evaporated concentration, crystallisation by cooling, isolated sodium chloride product and mother liquor I, mother liquor I return to step（1）It is molten to prepare mixing
Liquid A；NaCl mass percents content is 98.92% in the present embodiment sodium chloride product；
（4）According to the solid mass ratio 6 of water and solid sediment E liquid:1 ratio, is added water in reactor, in normal pressure, room
Under conditions of temperature, mixing speed are 500rpm, step is added（3）Gained solid sediment E, it is slow added into after sizing mixing uniformly
The phosphoric acid that mass concentration is 85% adjusts pH value of solution and to 2 and reacts 0.5h isolated solid sediment G and filtrate H, solid precipitation
Thing G obtains solid sediment I and cleaning solution J through water washing to neutrality, and solid sediment I is placed under the conditions of temperature is 150 DEG C and done
Dry 4h, it is subsequently placed under the conditions of temperature is 700 DEG C and is calcined 1.5h, cool down and produce phosphoric acid iron product；
After testing, Fe contents are 36.38% in phosphoric acid iron product in the present embodiment, P content 20.33%, and Fe and P mol ratio are
1:0.99, outward appearance is white.
Embodiment 3：A kind of method that accessory substance ferrophosphorus using industrial yellow phosphorus production prepares ferric phosphate, specific steps are such as
Under：
（1）Mixed solution A is prepared in the reactor（Mixed solution A is by the step of embodiment 1（4）Isolated mother liquor and water is matched somebody with somebody
Make and obtain）, then add and be ground to material all by the ferrophosphorus of 200 mesh sieves, be 80 DEG C, mixing speed in normal pressure, temperature
For Leach reaction 8h under conditions of 500rpm, isolated leachate B；Wherein the mass concentration of potassium chlorate is in mixed solution A
35%, the mass concentration of hydrochloric acid is 4%, and the solid mass ratio of liquid of mixed solution A and ferrophosphorus is 14:1；
（2）Under conditions of normal pressure, room temperature, mixing speed are 400rpm, in step（1）Sulfide is added in gained leachate B
（Sulfide is hydrogen sulfide saturated solution）And react 2.0h isolated solid sediment C and purifying filter liquor D；Wherein leachate B
The total mole number and sulfide of middle Pb, Cd, Hg, As, Cu metal ion（Hydrogen sulfide saturated solution）Middle S2-The molal quantity of ion
Than for 1:1.1；
（3）Under conditions of normal pressure, room temperature, mixing speed are 400rpm, in step（2）Quality is added in gained purifying filter liquor D
The sodium hydroxide solution of concentration 15%, regulation pH value of solution to 4, continue to react the isolated solid sediment E and filtrate F of 1.0h, filter
Liquid F is evaporated concentration, crystallisation by cooling, isolated sodium chloride product and mother liquor I, mother liquor I return to step（1）It is molten to prepare mixing
Liquid A；NaCl mass percents content is 98.67% in the present embodiment sodium chloride product；
（4）According to the solid mass ratio 4 of water and solid sediment E liquid:1 ratio, by the step of embodiment 1（4）Gained filtrate H and wash
The mixed solution for washing liquid J is added in reactor, under conditions of normal pressure, room temperature, mixing speed are 400rpm, adds step
（3）Gained solid sediment E, the phosphoric acid that mass concentration is 85% is slow added into after sizing mixing uniformly and adjusts pH value of solution to 1.5 and anti-
Answer 0.75h isolated solid sediment G and filtrate H, solid sediment G through water washing to neutrality obtain solid sediment I and
Cleaning solution J, solid sediment I are placed under the conditions of temperature is 120 DEG C and dry 6h, are subsequently placed under the conditions of temperature is 500 DEG C and are calcined
2.0h, cool down and produce phosphoric acid iron product；
After testing, Fe contents are 36.46% in phosphoric acid iron product in the present embodiment, P content 20.52%, Fe and P mol ratio
For 1:0.98, outward appearance is white.
Embodiment 4：A kind of method that accessory substance ferrophosphorus using industrial yellow phosphorus production prepares ferric phosphate, specific steps are such as
Under：
（1）Mixed solution A is prepared in the reactor（Mixed solution A is by the step of embodiment 2（4）Isolated mother liquor and water is matched somebody with somebody
Make and obtain）, then add and be ground to material all by the ferrophosphorus of 200 mesh sieves, be 95 DEG C, mixing speed in normal pressure, temperature
For Leach reaction 6.5h under conditions of 400rpm, isolated leachate B；The mass concentration of potassium chlorate wherein in mixed solution A
For 37%, the mass concentration of hydrochloric acid is 5%, and the solid mass ratio of liquid of mixed solution A and ferrophosphorus is 15:1；
（2）Under conditions of normal pressure, room temperature, mixing speed are 500rpm, in step（1）Sulfide is added in gained leachate B
（Sulfide is hydrogen sulfide saturated solution）And react 1.0h isolated solid sediment C and purifying filter liquor D；Wherein leachate B
The total mole number and sulfide of middle Pb, Cd, Hg, As, Cu metal ion（Hydrogen sulfide saturated solution）Middle S2-The molal quantity of ion
Than for 1:1.0；
（3）Under conditions of normal pressure, room temperature, mixing speed are 350rpm, in step（2）Quality is added in gained purifying filter liquor D
The sodium hydroxide solution of concentration 12%, regulation pH value of solution to 4.5, continue to react the isolated solid sediment E of 0.75h and filtrate
F, filtrate F are evaporated concentration, crystallisation by cooling, isolated sodium chloride product and mother liquor I, mother liquor I return to step（1）Prepare mixed
Close solution A；NaCl mass percents content is 98.84% in the present embodiment sodium chloride product；
（4）According to the solid mass ratio 6 of water and solid sediment E liquid:1 ratio, by the step of embodiment 2（4）Gained filtrate H and wash
The mixed solution for washing liquid J is added in reactor, under conditions of normal pressure, room temperature, mixing speed are 450rpm, adds step
（3）Gained solid sediment E, the phosphoric acid that mass concentration is 85% is slow added into after sizing mixing uniformly and adjusts pH value of solution to 2.0 and anti-
1.0h isolated solid sediment G and filtrate H, solid sediment G is answered to obtain solid sediment I through water washing to neutrality and wash
Liquid J is washed, solid sediment I is placed under the conditions of temperature is 130 DEG C and dries 6h, is subsequently placed under the conditions of temperature is 500 DEG C and is calcined
1.5h, cool down and produce phosphoric acid iron product；
After testing, Fe contents are 36.87% in phosphoric acid iron product in the present embodiment, P content 20.25%, Fe and P mol ratio
For 1:1.01, outward appearance is white.
Claims (4)
1. a kind of method that accessory substance ferrophosphorus using industrial yellow phosphorus production prepares ferric phosphate, it is characterised in that specific steps are such as
Under：
（1）Mixed solution A is prepared in the reactor, is then added and is ground to material all by the ferrophosphorus of 200 mesh sieves, normal
Leach reaction 6 ~ 8h, isolated leachate B under conditions of pressure, temperature are 80 ~ 95 DEG C, mixing speed is 300 ~ 500rpm；Its
Middle mixed solution A is the mixed aqueous solution of potassium chlorate and hydrochloric acid；
（2）According to the total mole number and S of Pb, Cd, Hg, As, Cu metal ion in solution2-The ratio of ion is 1: (1~
1.2) ratio, under conditions of normal pressure, room temperature, mixing speed are 300 ~ 500rpm, in step（1）Add in gained leachate B
Enter sulfide and react the isolated solid sediment C and purifying filter liquor D of 0.5~2.0h；
（3）Under conditions of normal pressure, room temperature, mixing speed are 300 ~ 500rpm, in step（2）Added in gained purifying filter liquor D
Sodium hydroxide solution, regulation pH value of solution continue 0.5 ~ 1.0h of reaction isolated solid sediment E and filtrate F, filtrate F to 4 ~ 6
It is evaporated concentration, crystallisation by cooling, isolated sodium chloride product and mother liquor I, mother liquor I return to step（1）Prepare mixed solution
A；
（4）Add water in reactor, under conditions of normal pressure, room temperature, mixing speed are 300 ~ 500rpm, add step
（3）Gained solid sediment E, phosphoric acid is slow added into after sizing mixing uniformly and adjusts pH value of solution to 1 ~ 2 and reacts 0.5 ~ 1.0h separation
Solid sediment G and filtrate H are obtained, solid sediment G obtains solid sediment I and cleaning solution J, solid through water washing to neutrality
Processing is dried in sediment I, is subsequently placed under the conditions of temperature is 500 ~ 700 DEG C and is calcined 1 ~ 2h, cools down and produce phosphoric acid iron product；
（5）By step（4）Gained filtrate H and cleaning solution J is well mixed return to step（4）Middle substitution water is added in reactor.
2. the method that the accessory substance ferrophosphorus produced according to claim 1 using industrial yellow phosphorus prepares ferric phosphate, its feature exist
In：Step（1）The mass concentration of potassium chlorate is 30 ~ 40% in mixed solution A, and the mass concentration of hydrochloric acid is 3 ~ 6%, mixed solution A
The solid mass ratio of liquid with ferrophosphorus is (12 ~ 16):1.
3. the method that the accessory substance ferrophosphorus produced according to claim 1 using industrial yellow phosphorus prepares ferric phosphate, its feature exist
In：Step（2）The sulfide added in leachate B is vulcanized sodium, phosphorus pentasulfide or hydrogen sulfide.
4. the method that the accessory substance ferrophosphorus produced according to claim 1 using industrial yellow phosphorus prepares ferric phosphate, its feature exist
In：Step（4）Reclaimed water and the solid sediment E solid mass ratio of liquid are (4 ~ 6):1.
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