CN115353429B - Method for preparing phosphate fertilizer by utilizing phosphate-containing iron tailings and obtained phosphate fertilizer - Google Patents
Method for preparing phosphate fertilizer by utilizing phosphate-containing iron tailings and obtained phosphate fertilizer Download PDFInfo
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- CN115353429B CN115353429B CN202210946152.5A CN202210946152A CN115353429B CN 115353429 B CN115353429 B CN 115353429B CN 202210946152 A CN202210946152 A CN 202210946152A CN 115353429 B CN115353429 B CN 115353429B
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- containing iron
- iron tailings
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002686 phosphate fertilizer Substances 0.000 title claims abstract description 30
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 26
- 239000010452 phosphate Substances 0.000 title claims abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000011574 phosphorus Substances 0.000 claims abstract description 91
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 91
- 238000000227 grinding Methods 0.000 claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims abstract description 13
- 230000003213 activating effect Effects 0.000 claims abstract description 11
- 238000005188 flotation Methods 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 17
- 238000004090 dissolution Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 15
- 239000000440 bentonite Substances 0.000 claims description 11
- 229910000278 bentonite Inorganic materials 0.000 claims description 11
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical group O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- -1 sodium phosphatidate Chemical class 0.000 claims description 2
- 239000002367 phosphate rock Substances 0.000 abstract description 16
- 230000008859 change Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003017 phosphorus Chemical class 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000004137 mechanical activation Methods 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 239000002994 raw material Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229940092782 bentonite Drugs 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 239000012467 final product Substances 0.000 description 4
- 229940080314 sodium bentonite Drugs 0.000 description 4
- 239000003337 fertilizer Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 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 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000013014 purified material Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940077441 fluorapatite Drugs 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a method for preparing phosphate fertilizer by utilizing phosphate-containing iron tailings and the obtained phosphate fertilizer, and relates to the technical field of comprehensive utilization of the phosphate-containing iron tailings. The invention uses the tailings containing the phosphorus with the phosphorus grade of about 10 percent and the effective phosphorus grade of about 3 percent to float and grind, then adds sodium stearate and an activating agent to mix into a planetary ball mill for grinding treatment, and the available phosphate fertilizer is obtained. The invention grinds the materials with high energy, and can improve the content of available phosphorus which can be directly absorbed by plants in the phosphate-containing iron tailings by utilizing the mechanical activation effect. The crystal structure of the superfine grinding activated phosphorus-containing iron tailings is changed to change the reactivity, and the superfine grinding activated phosphorus-containing iron tailings have the advantages of no pollution, high efficiency, low cost and simple operation in the reaction process, are suitable for treating the phosphorus-containing tailings and low-grade phosphorite, improve the effective phosphorus content of the phosphate-containing tailings and have an important effect on improving the utilization rate of phosphorus resources.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of phosphate-containing iron tailings, in particular to a method for preparing phosphate fertilizer by utilizing phosphate-containing iron tailings and the obtained phosphate fertilizer.
Background
In recent years, the grade of phosphate rock serving as a phosphate fertilizer raw material is reduced year by year, although the total phosphate rock resource of China is rich, the phosphate rock resource is unevenly distributed, most of northern areas lack phosphorus, the situation of 'north-south phosphorus delivery and east phosphorus adjustment' is formed by depending on the supply of Yunnan, guizhou and Hubei, the average grade of phosphorus is less than 17 percent by taking medium-low grade phosphate rock as a main material, most of ore except a few rich ores can be directly used as a phosphate chemical raw material, the purification is required, the selection ratio is larger when qualified concentrate is obtained due to the lower grade of phosphorus, the loss of phosphorus is larger in the sorting process, a great amount of tailings are produced while the utilization rate of phosphorus resources in the ore is reduced, and the environment is polluted.
The characteristic of common phosphate rock powder and superfine phosphate rock powder dissolved in different organic acids is disclosed in the document, that the superfine phosphate rock powder breaks the lattice structure of the phosphate rock powder through mechanical crushing, and the closely combined phosphorus is released, so that the phosphorus in the phosphate rock powder is fully utilized. However, the method adopts normal grade phosphate rock powder, has single component and no influence of other agents, only reveals the promotion mechanism of superfine grinding on the release of phosphorus in the phosphate rock powder, has no practical application scheme, ignores the influence of a plurality of external factors in the implementation and application process, defines the content of available phosphorus in national standard GB 20412-2006, and can be known that the available phosphorus is an attribute of the material, is irrelevant to the granularity of the material, the acid leaching adopted and the release speed of phosphorus, and is known to be different fields from the research of the patent.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing phosphate fertilizer by utilizing phosphate-containing iron tailings and the obtained phosphate fertilizer, wherein low-grade phosphate ores are prepared into usable phosphate fertilizer, and the comprehensive utilization rate of mineral products is improved.
In order to achieve the technical purpose, the invention adopts the following scheme:
a method for preparing phosphate fertilizer by utilizing phosphate-containing iron tailings comprises the following steps:
s1, flotation and purification of the phosphorus-containing iron tailings: the method comprises the steps of carrying out flotation and first grinding on the phosphate-containing iron tailings to obtain a first treated product with the full grain diameter smaller than 0.15 mm;
s2, secondary grinding: grinding the first treated material obtained in the step S1 for the second time to obtain a second treated material, wherein the content of the material with the thickness of-0.074 mm in the second treated material is 65-85%;
s3, adding an auxiliary agent: uniformly mixing the second treated matter, sodium stearate and an activating agent according to a proportion to obtain a third treated matter;
s4, superfine grinding: and (3) placing the third treated matter into a mill for superfine grinding to obtain the phosphate fertilizer with the full grain diameter less than 0.005 mm.
Further, the phosphorus grade in the phosphorus-containing iron tailings in the S1 is 10+/-1%, wherein the effective phosphorus grade is 3+/-1%, and the citrate dissolution rate is 30+/-5%.
Further, the flotation process of the phosphorus-containing iron tailings in the S1 comprises the following steps: adopting primary roughing and secondary concentration normal temperature flotation, wherein the concentration of ore pulp is 25-35%, and Na is used 2 CO 3 The pH value of the ore pulp is regulated to 8.5-9.5, the adopted collector is a combined collector, AW-01 (commercial product, manufacturer is a Hubei filial agent): the mass percentage of the oxidized paraffin soap is (80-90): 20-10%; the rough concentration reagent system is that the water glass dosage is 400-800 g/t, the combined collector dosage is 600-100 g/t, and the concentration reagent system is that the water glass dosage is 50-150 g/t. The phosphorus grade in the flotation concentrate is 20-25%, the effective phosphorus grade is 4-7%, and the citrate dissolution rate is 40+/-5%.
Further, a ball mill is adopted for the first grinding in the step S1, the rotating speed of the ball mill is 20-45/min, the concentration of ore pulp is 30-55%, and the grinding time is 3-6 min.
Further, in the step S2, a stirring mill is adopted for secondary grinding, the rotating speed of the stirring mill is 300-400 r/min, the pulp concentration is 45-65%, and the grinding time is 10-20 min.
Further, in the S3, the mass ratio of the second treatment substance to the sodium phosphatidate to the activating agent is (80-90)/(5-10)/(5-15).
Further, the activator is bentonite.
Further, the third grinding mill in the step S4 is a planetary ball mill, the rotating speed is 400-500 r/min, the pulp concentration is 45-55%, and the grinding time is 20-50 min.
The phosphorus grade in the phosphate fertilizer obtained by the method is 15% -20%, the effective phosphorus grade is 14% -16%, the citrate dissolution rate is 55% -70%, and compared with a mineral sample after flotation, the effective phosphorus grade is improved by 10% and the citrate dissolution rate is improved by 20%.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, by changing the utilization method of the low-grade phosphate rock, the phosphorus grade of the phosphate-containing iron tailings is properly improved through flotation, and then the phosphate rock after flotation is subjected to phosphorus activation release by using the grinding aid and the activating agent and is directly used as the phosphate fertilizer, so that the utilization rate of the low-grade phosphate rock is improved; the invention provides a method for utilizing phosphate-containing iron tailings with different conception, which aims to convert phosphorus which cannot be absorbed by soil and plants into citrate-soluble phosphorus after superfine grinding and activation of the phosphate-containing iron tailings, so that the phosphate ores can be directly used as phosphate fertilizers.
Drawings
FIG. 1 is a process flow diagram for preparing phosphate fertilizer by utilizing phosphate-containing iron tailings, which is provided by the embodiment of the invention;
FIG. 2 is a scanning electron microscope image of a first treatment and final product according to an embodiment of the present invention;
marked in the figure as: a-first treatment, b-final product.
Description of the embodiments
The present invention will be described in detail with reference to the following embodiments for a full understanding of the objects, features and effects of the present invention, but the present invention is not limited thereto.
At present, the traditional beneficiation method is generally adopted for the low-grade phosphorite activation, but the lower the grade of raw ore is, the larger the beneficiation ratio is when qualified concentrate is obtained, the larger the loss of phosphorus in the separation process is, so that the utilization rate of phosphorus resources in the ore is reduced, and a large amount of tailings are generated, thereby causing environmental pollution. Therefore, the application of a new technical means to activate the low-grade phosphorus-containing iron tailings is particularly important. The grinding process of the ore particles is essentially a process that mechanical energy is converted into internal energy so as to deform or break the particles, and when the energy generated by the action of mechanical force is applied to the object particles, the particle size of the object particles is reduced, the surface free energy is increased, and the crystallization state and the apparent morphology of the object particles are changed; the crystal structure of the phosphorus mineral is destroyed, so that the particles generate lattice distortion and amorphization, thereby improving the dissolving and releasing capacity of active ingredients in the low-grade phosphorus ore, namely increasing the content of the active ingredients, being capable of being directly used as a phosphorus fertilizer and improving the utilization rate of phosphorus ore resources.
FIG. 1 is a process flow diagram of the invention. As shown in fig. 1, the raw material is subjected to flotation purification treatment to improve the phosphorus grade of the phosphorus-containing iron tailings, so as to obtain a purified material, the purified material is subjected to first grinding by adopting a ball mill to obtain a first treated material, the first treated material is subjected to second grinding by adopting a stirring mill to obtain a second treated material with finer granularity, in order to further improve the utilization rate of phosphorus, sodium stearate, an activating agent and the second treated material are mixed according to a certain mass ratio to obtain a mixed material (third treated material), and finally the mixed material is subjected to superfine grinding activation by utilizing a planetary mill to obtain the product serving as the phosphate fertilizer.
The raw materials adopt the phosphorus-containing iron tailings in the Decode area, and the compositions are shown in table 1.
TABLE 1 elemental composition of phosphorus-containing iron tailings
Example 1
After the raw materials are subjected to a flotation process and a first ore grinding treatment, the phosphorus grade of the first treated material reaches 23%, the effective phosphorus grade reaches 5%, and the fineness of the first treated material is-0.15 mm and accounts for 100%. Grinding the first treated material by using a stirring mill to obtain a second treated material, wherein the granularity of the second treated material reaches-0.074 mm and the proportion is 74%. And mixing the second treated matter, sodium stearate and bentonite (activating agent) according to the mass ratio of 90:5:5 to obtain a third treated matter. And (3) putting the third treated matter into a planetary mill for grinding and mixing, wherein the rotation speed of the planetary mill is 500r/min, the ore pulp concentration is 55%, and the ore grinding time is 20min, so that the phosphate fertilizer product which can be directly used is obtained. The phosphorus grade in the phosphate fertilizer product is 18.5%, the effective phosphorus grade is 14.8%, and the citrate dissolution rate is 58%.
Example two
The raw material adopts the phosphorus-containing iron tailings in the Dewar area, the phosphorus grade of the first treated material reaches 23 percent after the flotation process and the first grinding treatment, the effective phosphorus grade reaches 5 percent, and the fineness of the first treated material is-0.15 mm and accounts for 100 percent. Grinding the first treated material by using a stirring mill to obtain a second treated material, wherein the granularity of the second treated material reaches-0.074 mm and the proportion is 74%. And mixing the second treated matter, sodium stearate and bentonite according to a mass ratio of 85:5:10 to obtain a third treated matter. And (3) putting the third treated matter into a planetary mill for grinding and mixing, wherein the rotation speed of the planetary mill is 500r/min, the ore pulp concentration is 55%, and the ore grinding time is 20min, so that the phosphate fertilizer product which can be directly used is obtained. The phosphorus grade in the product is 17.6%, the effective phosphorus grade is 15.2%, and the citrate dissolution rate is 62%.
Example III
The raw material adopts the phosphorus-containing iron tailings in the Dewar area, the phosphorus grade of the first treated material reaches 23 percent after the flotation process and the first grinding treatment, the effective phosphorus grade reaches 5 percent, and the fineness of the first treated material is-0.15 mm and accounts for 100 percent. Grinding the first treated material by using a stirring mill to obtain a second treated material, wherein the granularity of the second treated material reaches-0.074 mm and the proportion is 74%. And mixing the second treated matter, sodium stearate and bentonite according to a mass ratio of 80:5:15 to obtain a third treated matter. And (3) putting the third treated matter into a planetary mill for grinding and mixing, wherein the rotation speed of the planetary mill is 500r/min, the ore pulp concentration is 55%, and the ore grinding time is 20min, so that the phosphate fertilizer product which can be directly used is obtained. The phosphorus grade in the product is 16.9%, the effective phosphorus grade is 15.5%, and the citrate dissolution rate is 65%.
Example IV
The raw material adopts the phosphorus-containing iron tailings in the Dewar area, the phosphorus grade of the first treated material reaches 23 percent after the flotation process and the first grinding treatment, the effective phosphorus grade reaches 5 percent, and the fineness of the first treated material is-0.15 mm and accounts for 100 percent. Grinding the first treated material by using a stirring mill to obtain a second treated material, wherein the granularity of the second treated material reaches-0.074 mm and the proportion is 74%. And mixing the second treated matter, sodium stearate and bentonite according to a mass ratio of 80:10:10 to obtain a third treated matter. And (3) putting the third treated matter into a planetary mill for grinding and mixing, wherein the rotation speed of the planetary mill is 500r/min, the ore pulp concentration is 55%, and the ore grinding time is 20min, so that the phosphate fertilizer product which can be directly used is obtained. The phosphorus grade in the product is 16.7%, the effective phosphorus grade is 15.7%, and the citrate dissolution rate is 69%.
Comparative example 1 (Experimental example 1)
The raw material adopts the phosphorus-containing iron tailings in the Dewar area, the phosphorus grade of the first treated material reaches 23 percent after the flotation process and the first grinding treatment, the effective phosphorus grade reaches 5 percent, and the fineness of the first treated material is-0.15 mm and accounts for 100 percent. Grinding the first treated material by using a stirring mill to obtain a second treated material, wherein the granularity of the second treated material reaches-0.074 mm and the proportion is 74%. And mixing the second treated matter and bentonite according to the mass ratio of 90:5 to obtain a third treated matter. And (3) putting the third treated matter into a planetary mill for grinding and mixing, wherein the rotation speed of the planetary mill is 500r/min, the ore pulp concentration is 55%, and the ore grinding time is 20min, so that the phosphate fertilizer product which can be directly used is obtained. The phosphorus grade in the product is 18.7%, the effective phosphorus grade is 14.3%, and the citrate dissolution rate is 53%.
Comparative example 2 (with Experimental example one)
The raw material adopts the phosphorus-containing iron tailings in the Dewar area, the phosphorus grade of the first treated material reaches 23 percent after the flotation process and the first grinding treatment, the effective phosphorus grade reaches 5 percent, and the fineness of the first treated material is-0.15 mm and accounts for 100 percent. Grinding the first treated material by using a stirring mill to obtain a second treated material, wherein the granularity of the second treated material reaches-0.074 mm and the proportion is 74%. And mixing the second treated material and sodium stearate (grinding aid) according to a mass ratio of 90:5 to obtain a third treated material. And (3) putting the third treated matter into a planetary mill for grinding and mixing, wherein the rotation speed of the planetary mill is 500r/min, the ore pulp concentration is 55%, and the ore grinding time is 20min, so that the phosphate fertilizer product which can be directly used is obtained. The grade of phosphorus in the product is 18.9%, the grade of effective phosphorus is 14.5%, and the citrate dissolution rate is 55%.
Analysis of the products obtained in the examples and comparative examples:
(1) Structural analysis: the contact angle of the material is measured by a contact angle measuring instrument, the free energy of the surface is calculated, the morphological characteristics of the mineral sample are measured by a scanning electron microscope, and the change of the half-peak width and the change of the interplanar spacing are calculated by measuring the change of the crystal structure of the mineral sample by an X-ray diffraction technology.
The present invention provides a scanning electron microscope image (fig. 2), fig. 2a shows the phosphorus-containing iron tailings (first treated matter) before being activated, and fig. 2b shows the electron microscope image (final product) of the phosphorus fertilizer product finally obtained in the example.
The XRD diffraction results of the product are shown in table 1, in which half-width and interplanar spacing are exemplified by fluorapatite (211): determining the rotation speed of the planetary mill to be 500r/min, wherein the time is 20min, and under the condition that the ore pulp concentration is 55%, the number 1 is that the mass ratio of the phosphate-containing iron tailings to sodium stearate to bentonite (activating agent) is 90:5:5, mixing, wherein the number 2 is that the mass ratio of the phosphate-containing iron tailings to the sodium stearate to the bentonite is 80:5:15, mixing; the number 3 is that the mass ratio of the phosphate-containing iron tailings to the sodium stearate to the bentonite is 85:5:10, mixing, wherein the number 4 is that the mass ratio of the phosphate-containing iron tailings to sodium stearate to bentonite is 80:10: 10.
TABLE 1 data relating to the mill activated phosphate-containing iron tailings
| Numbering device | Particle diameter D50 (mum) | Surface free energy (mN/m) | Half-width (°) | Interplanar spacing (A) |
| 1 | 2.3 | 6.4 | 0.153 | 1.7321 |
| 2 | 1.9 | 7.5 | 0.155 | 1.7329 |
| 3 | 1.87 | 8.1 | 0.162 | 1.7340 |
| 4 | 1.75 | 9.2 | 0.170 | 1.7352 |
As shown in table 1, the surface free energy of the activated phosphate-containing iron tailings is gradually increased, and the surface activity of minerals is enhanced due to the activation; the half-width and the interplanar spacing were calculated to gradually increase, indicating that the diffraction peak was widened, the crystallinity was lowered, and lattice distortion occurred. Chemical analysis: the test conditions were the same as above, and the changes in available phosphorus grade and citrate dissolution rate (GB 20412-2006) in the end products of the examples and comparative examples were measured.
TABLE 2 effective phosphorus and citrate dissolution rate after grinding and activation
| Available phosphorus (%) | Rate of dissolution of citrate (%) | |
| Example 1 | 14.8 | 58 |
| Example 2 | 15.2 | 62 |
| Example 3 | 15.5 | 65 |
| Example 4 | 15.7 | 69 |
| Comparative example 1 | 14.3 | 53 |
| Comparative example 2 | 14.5 | 55 |
As is clear from the results in Table 2, the final product obtained in the present invention has a gradually reduced content of available phosphorus and a gradually increased citrate dissolution rate due to the gradual decrease of the added materials, compared with the raw material sample before the activation. Along with the combination of two-stage ore grinding and adding of grinding aid and activating agent, the phosphorus which can not be absorbed by soil and plants in the test process of the ore sample can be converted into phosphorus which can be directly absorbed and utilized by plants, namely, phosphorus with citrate dissolution rate.
Finally, it should be noted that: the above list is only a preferred embodiment of the present invention, and it is understood that those skilled in the art can make modifications and variations thereto, and it is intended that the present invention be construed as the scope of the appended claims and their equivalents.
Claims (2)
1. The method for preparing the phosphate fertilizer by utilizing the phosphate-containing iron tailings is characterized by comprising the following steps:
s1, flotation and purification of the phosphorus-containing iron tailings: the method comprises the steps of carrying out flotation and first grinding on the phosphate-containing iron tailings to obtain a first treated product with the full grain diameter smaller than 0.15 mm;
s2, secondary grinding: grinding the first treated material obtained in the step S1 for the second time to obtain a second treated material, wherein the content of the material with the thickness of-0.074 mm in the second treated material is 65-85%;
s3, adding an auxiliary agent: uniformly mixing the second treated matter, sodium stearate and an activating agent according to a proportion to obtain a third treated matter;
s4, superfine grinding: placing the third treated matter into a mill for superfine grinding to obtain the phosphate fertilizer with the full grain diameter less than 0.005 mm;
the grade of phosphorus in the phosphorus-containing iron tailings in S1 is 10+/-1%, wherein the grade of effective phosphorus is 3+/-1%, and the citrate dissolution rate is 30+/-5%;
the purification process of the phosphorus-containing iron tailings in the S1 adopts a primary roughing and secondary carefully selecting normal-temperature flotation process: the concentration of ore pulp is 25-35%, na is used for 2 CO 3 The pH value of the ore pulp is regulated to 8.5-9.5, and the adopted collector is a combined collector, AW-01: the mass percentage of the oxidized paraffin soap is (80-90): (20-10);
the coarse separation reagent system is that the water glass dosage is 400-800 g/t, the combined collector dosage is 600-100 g/t, the concentration reagent system is that the water glass dosage is 50-150 g/t, the phosphorus content in the flotation concentrate is 20-25%, the effective phosphorus content is 4-7%, and the citrate dissolution rate is 40+/-5%;
the mass ratio of the second treatment substance to the sodium phosphatidate to the activating agent in the S3 is (80-90): 5-10): 5-15;
the activating agent is bentonite;
s1, grinding for the first time by using a ball mill, wherein the rotating speed of the ball mill is 20-45/min, the concentration of ore pulp is 30-55%, and the grinding time is 3-6 min;
s2, carrying out secondary grinding by adopting a stirring mill, wherein the rotating speed of the stirring mill is 300-400 r/min, the concentration of ore pulp is 45-65%, and the grinding time is 10-20 min;
and S4, the third grinding mill is a planetary ball mill, the rotating speed is 400-500 r/min, the pulp concentration is 45-55%, and the grinding time is 20-50 min.
2. A phosphate fertilizer obtained by the method for preparing phosphate fertilizer from phosphate-containing iron tailings according to claim 1.
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| CN202110926447.1A CN113620743A (en) | 2021-08-12 | 2021-08-12 | Phosphate fertilizer and preparation method thereof |
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