CN114736061B - Method for producing compound fertilizer by using phosphate ore tailings - Google Patents
Method for producing compound fertilizer by using phosphate ore tailings Download PDFInfo
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- CN114736061B CN114736061B CN202210464792.2A CN202210464792A CN114736061B CN 114736061 B CN114736061 B CN 114736061B CN 202210464792 A CN202210464792 A CN 202210464792A CN 114736061 B CN114736061 B CN 114736061B
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 32
- 239000003337 fertilizer Substances 0.000 title claims abstract description 31
- 239000010452 phosphate Substances 0.000 title claims abstract description 31
- 150000001875 compounds Chemical class 0.000 title claims abstract description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 24
- 239000011343 solid material Substances 0.000 claims abstract description 20
- 239000002367 phosphate rock Substances 0.000 claims abstract description 14
- 239000006172 buffering agent Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 239000002440 industrial waste Substances 0.000 claims abstract description 11
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- STNSYZSNIYTNMI-UHFFFAOYSA-N azane;[2-[bis(phosphonomethyl)amino]ethyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound N.OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O STNSYZSNIYTNMI-UHFFFAOYSA-N 0.000 claims abstract description 8
- PZZHMLOHNYWKIK-UHFFFAOYSA-N eddha Chemical compound C=1C=CC=C(O)C=1C(C(=O)O)NCCNC(C(O)=O)C1=CC=CC=C1O PZZHMLOHNYWKIK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 7
- 239000000872 buffer Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract description 11
- 239000013522 chelant Substances 0.000 abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 abstract description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 3
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 3
- 230000036632 reaction speed Effects 0.000 abstract description 3
- 239000002738 chelating agent Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 24
- 239000000047 product Substances 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- -1 strontium aluminum sulfate Chemical compound 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002686 phosphate fertilizer Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LWNCNSOPVUCKJL-UHFFFAOYSA-N [Mg].[P] Chemical compound [Mg].[P] LWNCNSOPVUCKJL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 description 1
- 235000019785 monomagnesium phosphate Nutrition 0.000 description 1
- 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 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910052567 struvite Inorganic materials 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Fertilizers (AREA)
Abstract
The invention provides a method for producing compound fertilizer by using phosphate ore tailings, which comprises the following steps: grinding the phosphorite tailing raw material, putting the ground phosphorite tailing raw material into a reaction vessel, adding a buffering agent, adding industrial waste phosphoric acid until the pH value is less than or equal to 4.5, and stirring for 2-3h at 65-85 ℃; removing insoluble solids by solid-liquid separation, and slowly evaporating and crystallizing the rest solution at 50-60 ℃; and (3) carrying out solid-liquid separation again, washing the solid materials with water, and then drying the solid materials to obtain the compound fertilizer product. The invention adopts the industrial waste phosphoric acid as acidolysis raw material, and has low cost and environmental protection; according to the invention, EDTMPS, DTPMPA or EDDHA is used as a buffering agent, and the chelating agent and calcium and magnesium ions are subjected to chelating reaction to form a stable chelate, so that the metal chelate can flow in a solution due to a general flocculent structure, thus acid and internal raw materials are not blocked from further reaction, and the reaction speed and the final reaction degree are improved.
Description
Technical Field
The invention relates to the technical field of production of phosphorus-containing compound fertilizers, in particular to a method for producing a compound fertilizer by using phosphate ore tailings.
Background
Phosphorite is an important chemical mineral raw material. It can be used to prepare phosphate fertilizer, and also can be used to prepare yellow phosphorus, phosphoric acid, phosphide and other phosphates, and can be used in the industries of medicine, food, matches, dye, sugar, ceramics, national defense, etc. The phosphorite has been applied in industry for over a hundred years, and the known phosphorite-containing substances in nature are about 120 or more and are widely distributed. However, the quality and the quantity of the phosphorus-containing minerals can be achieved, and the phosphorus-containing minerals can be exploited and utilized. The main phosphorus-containing minerals used in industry for extracting phosphorus are apatite, and the secondary phosphorus-containing minerals include strontium aluminum sulfate, struvite, lan Tiedan and the like.
In the industrial exploitation process of phosphorite, impurities are removed through mineral separation, and high-quality raw materials rich in phosphorus elements are obtained so as to facilitate smelting production. In the mineral separation process, besides the high-quality raw materials, tailings containing impurities and a small amount of phosphorus elements are discharged, and the industrial treatment is carried out to prepare phosphoric acid or phosphate fertilizer without economic value because the content of the phosphorus elements in the tailings is low and the content of harmful impurities is high, so that a large amount of phosphate tailings are not utilized and even are discarded. The large-scale accumulation of the phosphorite tailings not only occupies large-area land and farmland resources, but also consumes more yard construction and maintenance cost; in addition, the environment-friendly solar energy storage tank is stored in the open air, and is subjected to wind blowing, sun drying and rain leaching for a long time, so that harmful components can destroy the ecological environment through the mediums such as the atmosphere, the soil surface or the underground water, and serious pollution is caused to the environment.
At present, the utilization of phosphorite tailings mainly uses tailings sand as roadbed filler, produces bricks for walls, chemically produces phosphorus-magnesium compound fertilizer and the like. In the field of producing compound fertilizer by utilizing phosphate tailings, the most commonly used method is to dissolve solid tailings by sulfuric acid to obtain water-soluble sulfate, and obtain the water-soluble compound fertilizer after solid-liquid separation. However, this approach has certain problems. Firstly, the price of the sulfuric acid used as a raw material is low, a large amount of sulfuric acid is consumed in the dissolution process, and the production cost is increased. Secondly, as the phosphate tailings generally contain calcium and magnesium elements, if sulfuric acid is used for dissolution, calcium sulfate precipitation can be generated on the surfaces of raw material particles, so that the contact between the raw materials and acid is prevented, and the reaction degree and reaction speed are reduced; if phosphoric acid is used for dissolution in order to save cost, magnesium phosphate precipitates are formed, and the dissolution reaction is also not facilitated.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a method for producing compound fertilizer by using phosphate ore tailings, which solves the problems that the acidolysis cost is higher by using sulfuric acid and the generated precipitate prevents the reaction from further proceeding in the prior art.
According to an embodiment of the invention, a method for producing a compound fertilizer by using phosphate ore tailings comprises the following steps:
s1, grinding a phosphorite tailing raw material, putting the ground phosphorite tailing raw material into a reaction vessel, then adding a buffer with the mass of 5-8% of the raw material, adding industrial waste phosphoric acid until the pH value is less than or equal to 4.5, and stirring for 2-3 hours at 65-85 ℃;
s2, carrying out solid-liquid separation on the mixed solution to remove insoluble solids, and then slowly evaporating and crystallizing the rest solution at 50-60 ℃ until all products in the solution are separated out;
s3, carrying out solid-liquid separation again to remove the residual acid solution, then washing the solid material until the pH value of the discharged washing liquid is more than or equal to 6.5, and then drying the solid material to obtain the compound fertilizer product.
Preferably, the grinding fineness of the phosphorite tailing raw material is less than or equal to 200 meshes.
Preferably, the buffer is one of EDTMPS, DTPMPA or EDDHA.
Further, the insoluble solids removed in step S2 are washed with water, and the washed liquid is incorporated into the remaining solution.
In step S2, solid-liquid separation is performed by centrifugation, and the solid sediment is collected and then the upper solution is discharged.
Further, in the step S3, solid-liquid separation is performed by vacuum filtration.
Further, the cleaning liquid in the step S3 is introduced into a waste phosphoric acid tank for recovery.
Further, the solid material in the step S3 is subjected to pneumatic drying at 80-90 ℃.
The technical principle of the invention is as follows: according to the invention, a buffering agent is added into the raw materials, then acid is added into the raw materials for mixing, and phosphoric acid reacts with phosphate tailings to generate monocalcium phosphate and magnesium dihydrogen phosphate, so that a stable solution is formed; at this time, the dissolved calcium and magnesium ions react with the buffering agent to form chelate firstly, insoluble or slightly soluble precipitate is avoided from being directly formed with anions of sulfate radical and phosphate radical, thus, the precipitate is not covered on the surface of the raw material to prevent the subsequent dissolution, after the reaction is continuously carried out, all phosphate tailings are dissolved, the excessive hydrogen ions enable the whole solution to be acidic, so that the metal ions can remain in the form of chelate to be in a solution system, and solid products are formed in the process of subsequent evaporation and crystallization.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the prior art that sulfuric acid is adopted for dissolution, the method has the advantage of low cost, can treat industrial waste phosphoric acid, is equivalent to simultaneously recovering and treating waste phosphate tailings and phosphoric acid, and has a very large green and environment-friendly function;
2. according to the invention, EDTMPS, DTPMPA or EDDHA is used as a buffering agent, and the chelating agent and calcium and magnesium ions are subjected to chelating reaction to form a stable chelate, so that the metal chelate is generally flocculent, can not be tightly adsorbed on the surfaces of raw material particles, but can flow in a solution, thus acid and internal raw materials can not be blocked from further reaction, and the reaction speed and the final reaction degree are improved.
Detailed Description
The technical scheme of the invention is further described below by referring to examples.
Example 1:
the embodiment provides a method for producing a compound fertilizer by using phosphate ore tailings, which comprises the following steps:
s1, grinding 2t of phosphate ore tailing raw materials to 200 meshes, then adding into a reaction vessel, then adding 5 wt% of buffering agent which is EDTMPS in the embodiment, adding industrial waste phosphoric acid until the pH value is less than or equal to 4.5, and stirring for 3 hours at 65 ℃;
s2, performing solid-liquid separation on the mixed solution by adopting a centrifugal method, discharging an upper solution after solid sediment is gathered so as to separate insoluble solids, washing the insoluble solids with water, and merging the washed liquid into the residual solution; then slowly evaporating and crystallizing the rest solution at 50 ℃ until the products in the solution are totally separated out;
s3, performing solid-liquid separation by using vacuum suction filtration to remove residual acid solution, then washing the solid material until the pH value of the discharged washing liquid is more than or equal to 6.5, introducing the washing liquid into a waste phosphoric acid tank for recycling, and then performing air flow drying on the solid material at 80 ℃ to obtain a compound fertilizer product.
Example 2:
the embodiment provides a method for producing a compound fertilizer by using phosphate ore tailings, which comprises the following steps:
s1, grinding 2t of phosphate ore tailing raw materials to 180 meshes, then adding into a reaction vessel, then adding 7 wt% of buffering agent which is EDTMPS in the embodiment, adding industrial waste phosphoric acid until the pH value is less than or equal to 4.5, and stirring for 2.5 hours at 75 ℃;
s2, performing solid-liquid separation on the mixed solution by adopting a centrifugal method, discharging an upper solution after solid sediment is gathered so as to separate insoluble solids, washing the insoluble solids with water, and merging the washed liquid into the residual solution; then slowly evaporating and crystallizing the rest solution at 55 ℃ until the products in the solution are totally separated out;
s3, performing solid-liquid separation by using vacuum suction filtration to remove residual acid solution, then washing the solid material until the pH value of the discharged washing liquid is more than or equal to 6.5, introducing the washing liquid into a waste phosphoric acid tank for recycling, and then performing air flow drying on the solid material at 85 ℃ to obtain a compound fertilizer product.
Example 3:
the embodiment provides a method for producing a compound fertilizer by using phosphate ore tailings, which comprises the following steps:
s1, grinding 2t of phosphate ore tailing raw materials to 160 meshes, then adding into a reaction vessel, then adding 8 wt% of buffering agent which is EDTMPS in the embodiment, adding industrial waste phosphoric acid until the pH value is less than or equal to 4.5, and stirring for 2 hours at 85 ℃;
s2, performing solid-liquid separation on the mixed solution by adopting a centrifugal method, discharging an upper solution after solid sediment is gathered so as to separate insoluble solids, washing the insoluble solids with water, and merging the washed liquid into the residual solution; then slowly evaporating and crystallizing the rest solution at 60 ℃ until the products in the solution are totally separated out;
s3, performing solid-liquid separation by using vacuum suction filtration to remove residual acid solution, then washing the solid material until the pH value of the discharged washing liquid is more than or equal to 6.5, introducing the washing liquid into a waste phosphoric acid tank for recycling, and then performing air flow drying on the solid material at 90 ℃ to obtain a compound fertilizer product.
Example 4:
the embodiment provides a method for producing a compound fertilizer by using phosphate ore tailings, which comprises the following steps:
s1, grinding 2t of phosphate ore tailing raw materials to 160 meshes, then adding into a reaction vessel, then adding a buffering agent with the mass of 8% by weight into the reaction vessel, wherein the buffering agent in the embodiment is DTPMPA, adding industrial waste phosphoric acid until the pH value is less than or equal to 4.5, and stirring for 2 hours at the temperature of 85 ℃;
s2, performing solid-liquid separation on the mixed solution by adopting a centrifugal method, discharging an upper solution after solid sediment is gathered so as to separate insoluble solids, washing the insoluble solids with water, and merging the washed liquid into the residual solution; then slowly evaporating and crystallizing the rest solution at 60 ℃ until the products in the solution are totally separated out;
s3, performing solid-liquid separation by using vacuum suction filtration to remove residual acid solution, then washing the solid material until the pH value of the discharged washing liquid is more than or equal to 6.5, introducing the washing liquid into a waste phosphoric acid tank for recycling, and then performing air flow drying on the solid material at 90 ℃ to obtain a compound fertilizer product.
Example 5:
the embodiment provides a method for producing a compound fertilizer by using phosphate ore tailings, which comprises the following steps:
s1, grinding 2t of phosphate ore tailing raw materials to 160 meshes, then adding into a reaction vessel, then adding a buffering agent with the mass of 8% by weight of the raw materials, wherein the buffering agent is EDDHA in the embodiment, adding industrial waste phosphoric acid until the pH value is less than or equal to 4.5, and stirring for 2 hours at the temperature of 85 ℃;
s2, performing solid-liquid separation on the mixed solution by adopting a centrifugal method, discharging an upper solution after solid sediment is gathered so as to separate insoluble solids, washing the insoluble solids with water, and merging the washed liquid into the residual solution; then slowly evaporating and crystallizing the rest solution at 60 ℃ until the products in the solution are totally separated out;
s3, performing solid-liquid separation by using vacuum suction filtration to remove residual acid solution, then washing the solid material until the pH value of the discharged washing liquid is more than or equal to 6.5, introducing the washing liquid into a waste phosphoric acid tank for recycling, and then performing air flow drying on the solid material at 90 ℃ to obtain a compound fertilizer product.
Comparative example 6:
the comparative example provides a method for producing a compound fertilizer by using phosphate ore tailings, which comprises the following steps:
s1, grinding 2t of phosphate ore tailing raw materials to 160 meshes, then adding into a reaction vessel, adding industrial waste phosphoric acid until the pH value is less than or equal to 4.5, and stirring for 2 hours at the temperature of 85 ℃;
s2, performing solid-liquid separation on the mixed solution by adopting a centrifugal method, discharging an upper solution after solid sediment is gathered so as to separate insoluble solids, washing the insoluble solids with water, and merging the washed liquid into the residual solution; then slowly evaporating and crystallizing the rest solution at 60 ℃ until the products in the solution are totally separated out;
s3, performing solid-liquid separation by using vacuum suction filtration to remove residual acid solution, then washing the solid material until the pH value of the discharged washing liquid is more than or equal to 6.5, introducing the washing liquid into a waste phosphoric acid tank for recycling, and then performing air flow drying on the solid material at 90 ℃ to obtain a compound fertilizer product.
The product parameters obtained in examples 1-5 and comparative example 6 are compared by table 1.
Raw material dissolution ratio after 2h of reaction | Total yield of product | |
Example 1 | 86.5% | 88.4% |
Example 2 | 91.6% | 87.8% |
Example 3 | 97.2% | 87.3% |
Example 4 | 96.4% | 87.1% |
Example 5 | 95.8% | 87.2% |
Comparative example 6 | 36.3% | 74.5% |
TABLE 1
As can be seen from Table 1, the dissolution rate of the raw materials and the overall yield of the products in examples 1 to 5 of the present invention are far superior to those in comparative example 6, and it is fully demonstrated that the surface coverage precipitation of the raw materials can be avoided by the chelating reaction after the addition of the buffer, thereby allowing the acidolysis reaction to proceed continuously and stably.
In addition, examples 1 to 3 were different in dissolution rate due to the difference in reaction temperature and time, and the yield was relatively high in the case of longer reaction time although the reaction rate was faster in the case of high temperature.
Examples 3 to 5 used the same reaction conditions except that the buffer used was different, and the chelate constant of EDTMPS, DTPMPA, EDDHA was decreased in order, so that the stability of chelate formation with metal ions was decreased in order, resulting in increased formation of precipitated metal ions and decreased reaction rate.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (6)
1. The method for producing the compound fertilizer by using the phosphate ore tailings is characterized by comprising the following steps:
s1, grinding a phosphate rock tailing raw material, then adding the ground phosphate rock tailing raw material into a reaction vessel, wherein the grinding fineness of the phosphate rock tailing raw material is less than or equal to 200 meshes, then adding a buffering agent with the mass of 5-8% by weight of the raw material, adding industrial waste phosphoric acid until the pH value is less than or equal to 4.5, and stirring for 2-3 hours at the temperature of 65-85 ℃;
s2, carrying out solid-liquid separation on the mixed solution to remove insoluble solids, and then slowly evaporating and crystallizing the rest solution at 50-60 ℃ until all products in the solution are separated out;
s3, carrying out solid-liquid separation again to remove the residual acid solution, then washing the solid material until the pH value of the discharged washing liquid is more than or equal to 6.5, and then drying the solid material to obtain a compound fertilizer product;
the buffer is one of EDTMPS or EDDHA.
2. A method for producing a compound fertilizer using phosphate tailings as claimed in claim 1, wherein: the insoluble solids removed in step S2 are washed with water and the washed liquid is incorporated into the remaining solution.
3. A method for producing a compound fertilizer using phosphate tailings as claimed in claim 1, wherein: and in the step S2, solid-liquid separation is carried out by adopting a centrifugal method, and the solid sediment is gathered and then the upper solution is discharged.
4. A method for producing a compound fertilizer using phosphate tailings as claimed in claim 1, wherein: in the step S3, solid-liquid separation is performed by vacuum filtration.
5. A method for producing a compound fertilizer using phosphate tailings as claimed in claim 1, wherein: and (3) introducing the cleaning liquid in the step (S3) into a waste phosphoric acid tank for recycling.
6. A method for producing a compound fertilizer using phosphate tailings as claimed in claim 1, wherein: the solid material in the step S3 is subjected to pneumatic drying at 80-90 ℃.
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CN110124851A (en) * | 2019-04-30 | 2019-08-16 | 东北大学 | A method of the decalcification of magnesite ore inverse flotation is carried out using EDDHA inhibitor |
CN110423148A (en) * | 2018-11-27 | 2019-11-08 | 湖北新洋丰肥业股份有限公司 | A method of amino acid Water soluble fertilizer is prepared using High-Mg phosphate tailings |
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CN1924046A (en) * | 2006-08-25 | 2007-03-07 | 四川大学 | Method of retrieving magnesium from high magnesium phosphorus ore |
CN110423148A (en) * | 2018-11-27 | 2019-11-08 | 湖北新洋丰肥业股份有限公司 | A method of amino acid Water soluble fertilizer is prepared using High-Mg phosphate tailings |
CN110124851A (en) * | 2019-04-30 | 2019-08-16 | 东北大学 | A method of the decalcification of magnesite ore inverse flotation is carried out using EDDHA inhibitor |
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