CN105502318A - Method for dissolving low- and medium-grade phosphorite by utilizing phosphorite pit water microbial flora - Google Patents
Method for dissolving low- and medium-grade phosphorite by utilizing phosphorite pit water microbial flora Download PDFInfo
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- CN105502318A CN105502318A CN201610064930.2A CN201610064930A CN105502318A CN 105502318 A CN105502318 A CN 105502318A CN 201610064930 A CN201610064930 A CN 201610064930A CN 105502318 A CN105502318 A CN 105502318A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/01—Treating phosphate ores or other raw phosphate materials to obtain phosphorus or phosphorus compounds
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Abstract
The invention relates to a method for dissolving low- and medium-grade phosphorite by using phosphorite pit water microbial flora. The method comprises the following steps: (1) enrichment cultivation of phosphorite pit water microbial flora: performing enrichment cultivation on the phosphorite pit water microbial flora to obtain a phosphorite pit water microbial flora enrichment culture solution; (2) dissolving of the low- and medium-grade phosphorite by using the phosphorite pit water microbial flora: adding a non-phosphorus culture medium and the low- and medium-grade phosphorite into a container, and then adding the phosphorite pit water microbial flora enrichment culture solution for cultivation. The method is simple technologically, low in requirement on cultivation condition and environment-friendly; the low- and medium-grade phosphorite solubilization efficiency is over 60 percent. The microbial flora is from phosphorite pit water, and is high in phosphorite environment adaptability, so that microbial acclimation cultivation is not needed.
Description
Technical field
The present invention relates to phosphorate rock mining processing technique field, particularly relate to a kind of method utilizing phosphorus ore pit water microorganism species to dissolve mid low grade phosphate rock.
Background technology
China is the country that a phosphate rock resource enriches, but major part is all mid low grade phosphate rock.In China's phosphorus ore proven reserve, phosphorus ore average grade is about about 17%, and the rich ore that ore grade is greater than 30% is no more than 10% of total reserves.Ore grade is thin lower than the mid low grade phosphate rock ore disseminated grain size of 30%, and mineral composition is complicated, and foreign matter content is high.These factors determine when adopting conventional wet or these mid low grade phosphate rocks of thermal process phosphatic fertilizer production technique process, and production cost is high, low in economic efficiency.
The development mode that what current China most of phosphate rockmining enterprise adopted is " adopting richness abandons poor ", if according to present exploitation scale, the existing rich phosphate rock resource of China will at several years internal consumptions totally, and the more weak problem of the phosphate rock resource supportability of China is by outstanding day by day.One of 20 mineral that can not meet national economic development requirement after phosphorus ore is classified as 2010 by Ministry of Land and Resources.Therefore, how to strengthen the exploitation of China's Mid-and low-grade phosphate rock resources, for scientific utilization resource, improve the level of resources utilization and maintain the sustainable health development of domestic Phosphate Fertilizer Industry significant.
Based on reducing costs, economizing on resources and day by day serious environmental issue, many investigators make full use of the new way of Mid-and low-grade phosphate rock resources at positive reasonable, such as biological method.Microorganism plays keying action in the circulation of nature phosphorus, and occurring in nature also exists the molten phosphorus microorganism of substantial amounts.In recent years, molten phosphorus microorganism is utilized to dissolve mid low grade phosphate rock as inoculum and the research being translated into titanium pigment has caused people more and more pays close attention to.Although the research at present in biosolubilization mid low grade phosphate rock achieves some good progress, but also there is certain deficiency, namely current research adopts several bacterial classification that is single or principal component mostly, the rare research utilizing microorganism species that is natural, non-principal component to dissolve mid low grade phosphate rock.The present invention utilizes phosphorus ore pit water microorganism species to dissolve mid low grade phosphate rock, and bacterial classification does not need to cultivate through domestication, simplifies production technique and improves molten phosphorus rate.
Summary of the invention
The object of the present invention is to provide a kind of method utilizing phosphorus ore pit water microorganism species to dissolve mid low grade phosphate rock, the method has the features such as molten phosphorus rate is high, bacterial classification is cultivated without the need to domestication, technique is simple, culture condition requirement is low, production cost is low.
To achieve these goals, technical scheme of the present invention is as follows:
A kind of method utilizing phosphorus ore pit water microorganism species to dissolve mid low grade phosphate rock, comprise the steps: 1) enrichment culture of phosphorus ore pit water microorganism species: phosphorus ore pit water microorganism species is carried out enrichment culture, obtains phosphorus ore pit water microorganism species enrichment culture liquid; 2) phosphorus ore pit water microorganism species enrichment culture liquid dissolves mid low grade phosphate rock: without phosphorus substratum and mid low grade phosphate rock are added in container, then adds phosphorus ore pit water microorganism species enrichment culture liquid and cultivate.
Step 1) enrichment culture of described phosphorus ore pit water microorganism species comprise a will have phosphorus substratum and phosphorus ore pit water by volume 1:0.5-0.8 load in container, container is placed in constant-temperature table shaking culture, obtains phosphorus ore pit water microorganism species enrichment culture liquid A; B will have in phosphorus substratum and phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.5-0.8 loading by volume container, container will be placed in constant-temperature table shaking culture, obtain the phosphorus ore pit water microorganism species enrichment culture liquid A of enrichment again; C repeating step b1-3 time, obtains phosphorus ore pit water microorganism species enrichment culture liquid.
Constant-temperature table temperature is 22-30 DEG C, and rotating speed is 100-160 rev/min, and the shaking culture time is 3-5 days.
Step 2) described phosphorus ore pit water microorganism species enrichment culture liquid dissolve mid low grade phosphate rock comprise by without phosphorus substratum and phosphorus ore pit water microorganism species enrichment culture liquid by volume 1:0.2-0.3 load in container, 10-20g mid low grade phosphate rock is added again by the without phosphorus substratum of every 1000ml, container is placed in 22-30 DEG C of constant-temperature table after mixing, shaking culture 7-10 days under 120-160 rev/min of rotating speed.
Described without phosphorus substratum consists of 10g/L glucose, 0.5g/L yeast extract, 0.5g/L (NH
4)
2sO
4, 0.2g/LKCl, 0.1g/LMgSO
47H
2o, 0.0001g/LMnSO
4h
2o, 0.0001g/LFeSO
47H
2o, solvent is sterilized water.
Described have phosphorus substratum to consist of 10g/L glucose, 0.5g/L yeast extract, 0.5g/L (NH
4)
2sO
4, 0.2g/LKCl, 0.1g/LMgSO
47H
2o, 0.0001g/LMnSO
4h
2o, 0.0001g/LFeSO
47H
2the calcium phosphate of O, 10-20g/L, solvent is sterilized water.
In described mid low grade phosphate rock, the mass content of Vanadium Pentoxide in FLAKES is lower than 30%, and described mid low grade phosphate rock needs to be crushed to particle diameter for 50-200 order before using.
The invention has the beneficial effects as follows:
1, in the present invention, microorganism species is from phosphorus ore pit water, and it is strong to phosphorus ore environmental compatibility, does not need to carry out microbial acclimation cultivation, simplifies technique and substantially increase production efficiency.
2, the molten phosphorus rate of the method to mid low grade phosphate rock can reach more than 60%, and the scientific utilization for the Mid-and low-grade phosphate rock resources of China's abundant provides a practicable method.
3, present invention process is simple, culture condition requirement is low, and environmental friendliness.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
The without phosphorus nutrient media components that the present invention and embodiment adopt is: 10g glucose, 0.5g yeast extract, 0.5g (NH
4)
2sO
4, 0.2gKCl, 0.1gMgSO
47H
2o, 0.0001gMnSO
4h
2o, 0.0001gFeSO
47H
2o and 1000mL sterilized water.Described have phosphorus substratum to be that in aforementioned without phosphorus substratum, add the calcium phosphate of 10-20g/L formulated.
Embodiment 1
Utilize phosphorus ore pit water microorganism species to dissolve a method for mid low grade phosphate rock, comprise the steps:
1) enrichment culture of phosphorus ore pit water microorganism species: will have phosphorus substratum and phosphorus ore pit water by volume 1:0.8 load in container (as triangular flask), container is placed in 22 DEG C of constant-temperature tables shaking culture 4 days under the rotating speed of 140 revs/min, obtains the phosphorus ore pit water microorganism species enrichment culture liquid A of the 1st enrichment culture.
To have in the phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.7 loading by volume container of phosphorus substratum and the 1st enrichment culture, container is placed in 30 DEG C of constant-temperature tables shaking culture 5 days under the rotating speed of 100 revs/min, obtains the phosphorus ore pit water microorganism species enrichment culture liquid A of the 2nd enrichment culture.
To have in the phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.7 loading by volume container of phosphorus substratum and the 2nd enrichment culture, container is placed in 25 DEG C of constant-temperature tables shaking culture 4 days under the rotating speed of 140 revs/min, obtains the phosphorus ore pit water microorganism species enrichment culture liquid A of the 3rd enrichment culture.
To have in the phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.5 loading by volume container of phosphorus substratum and the 3rd enrichment culture, container is placed in 22 DEG C of constant-temperature tables shaking culture 3 days under the rotating speed of 140 revs/min, obtains phosphorus ore pit water microorganism species enrichment culture liquid (namely so repeatedly inoculating enrichment culture 4 times).
2) phosphorus ore pit water microorganism species enrichment culture liquid dissolves mid low grade phosphate rock: add in container by without phosphorus substratum and mid low grade phosphate rock, add phosphorus ore pit water microorganism species enrichment culture liquid again to mix, container is placed in 25 DEG C of constant-temperature tables afterwards, under 160 revs/min of rotating speeds, shaking culture obtains titanium pigment in 10 days.Wherein the volume ratio of without phosphorus substratum and phosphorus ore pit water microorganism species enrichment culture liquid is 1:0.2, and the without phosphorus substratum of every 1000ml adds 20g mid low grade phosphate rock.
In the mid low grade phosphate rock that the present embodiment adopts, the mass content of Vanadium Pentoxide in FLAKES is 29.7%, and molten phosphorus rate reaches 78.5%.
Embodiment 2
Utilize phosphorus ore pit water microorganism species to dissolve a method for mid low grade phosphate rock, comprise the steps:
1) enrichment culture of phosphorus ore pit water microorganism species: will have phosphorus substratum and phosphorus ore pit water by volume 1:0.7 load in container (as triangular flask), container is placed in 25 DEG C of constant-temperature tables shaking culture 4 days under the rotating speed of 120 revs/min, obtains the phosphorus ore pit water microorganism species enrichment culture liquid A of the 1st enrichment culture.
To have in the phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.7 loading by volume container of phosphorus substratum and the 1st enrichment culture, container is placed in 25 DEG C of constant-temperature tables shaking culture 4 days under the rotating speed of 120 revs/min, obtains the phosphorus ore pit water microorganism species enrichment culture liquid A of the 2nd enrichment culture.
To have in the phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.7 loading by volume container of phosphorus substratum and the 2nd enrichment culture, container is placed in 25 DEG C of constant-temperature tables shaking culture 4 days under the rotating speed of 120 revs/min, obtains the phosphorus ore pit water microorganism species enrichment culture liquid A of the 3rd enrichment culture.
To have in the phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.7 loading by volume container of phosphorus substratum and the 3rd enrichment culture, container is placed in 25 DEG C of constant-temperature tables shaking culture 4 days under the rotating speed of 120 revs/min, obtains phosphorus ore pit water microorganism species enrichment culture liquid (namely so repeatedly inoculating enrichment culture 4 times).
2) phosphorus ore pit water microorganism species enrichment culture liquid dissolves mid low grade phosphate rock: add in container by without phosphorus substratum and mid low grade phosphate rock, add phosphorus ore pit water microorganism species enrichment culture liquid again to mix, container is placed in 30 DEG C of constant-temperature tables afterwards, under 140 revs/min of rotating speeds, shaking culture obtains titanium pigment in 8 days.Wherein the volume ratio of without phosphorus substratum and phosphorus ore pit water microorganism species enrichment culture liquid is 1:0.25, and the without phosphorus substratum of every 1000ml adds 15g mid low grade phosphate rock.
In the mid low grade phosphate rock that the present embodiment adopts, the mass content of Vanadium Pentoxide in FLAKES is 22.6%, and molten phosphorus rate reaches 71.4%.
Embodiment 3
Utilize phosphorus ore pit water microorganism species to dissolve a method for mid low grade phosphate rock, comprise the steps:
1) enrichment culture of phosphorus ore pit water microorganism species: will have phosphorus substratum and phosphorus ore pit water by volume 1:0.5 load in container (as triangular flask), container is placed in 25 DEG C of constant-temperature tables shaking culture 3 days under the rotating speed of 160 revs/min, obtains the phosphorus ore pit water microorganism species enrichment culture liquid A of the 1st enrichment culture.
To have in the phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.6 loading by volume container of phosphorus substratum and the 1st enrichment culture, container is placed in 30 DEG C of constant-temperature tables shaking culture 5 days under the rotating speed of 120 revs/min, obtains the phosphorus ore pit water microorganism species enrichment culture liquid A of the 2nd enrichment culture.
To have in the phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.7 loading by volume container of phosphorus substratum and the 2nd enrichment culture, container is placed in 22 DEG C of constant-temperature tables shaking culture 3 days under the rotating speed of 140 revs/min, obtains the phosphorus ore pit water microorganism species enrichment culture liquid A of the 3rd enrichment culture.
To have in the phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.6 loading by volume container of phosphorus substratum and the 3rd enrichment culture, container is placed in 28 DEG C of constant-temperature tables shaking culture 4 days under the rotating speed of 130 revs/min, obtains the phosphorus ore pit water microorganism species enrichment culture liquid A of the 4th enrichment culture.
To have in the phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.5 loading by volume container of phosphorus substratum and the 4th enrichment culture, container is placed in 22 DEG C of constant-temperature tables shaking culture 4 days under the rotating speed of 150 revs/min, obtains phosphorus ore pit water microorganism species enrichment culture liquid (namely so repeatedly inoculating enrichment culture 5 times).
2) phosphorus ore pit water microorganism species enrichment culture liquid dissolves mid low grade phosphate rock: add in container by without phosphorus substratum and mid low grade phosphate rock, add phosphorus ore pit water microorganism species enrichment culture liquid again to mix, container is placed in 25 DEG C of constant-temperature tables afterwards, under 140 revs/min of rotating speeds, shaking culture obtains titanium pigment in 7 days.Wherein the volume ratio of without phosphorus substratum and phosphorus ore pit water microorganism species enrichment culture liquid is 1:0.3, and the without phosphorus substratum of every 1000ml adds 10g mid low grade phosphate rock.
In the mid low grade phosphate rock that the present embodiment adopts, the mass content of Vanadium Pentoxide in FLAKES is 28.2%, and molten phosphorus rate reaches 69.5%.
Embodiment 4
Utilize phosphorus ore pit water microorganism species to dissolve a method for mid low grade phosphate rock, comprise the steps:
1) enrichment culture of phosphorus ore pit water microorganism species: will have phosphorus substratum and phosphorus ore pit water by volume 1:0.6 load in container (as triangular flask), container is placed in 30 DEG C of constant-temperature tables shaking culture 5 days under the rotating speed of 100 revs/min, obtains the phosphorus ore pit water microorganism species enrichment culture liquid A of the 1st enrichment culture.
To have in the phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.7 loading by volume container of phosphorus substratum and the 1st enrichment culture, container is placed in 22 DEG C of constant-temperature tables shaking culture 5 days under the rotating speed of 160 revs/min, obtains the phosphorus ore pit water microorganism species enrichment culture liquid A of the 2nd enrichment culture.
To have in the phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.8 loading by volume container of phosphorus substratum and the 2nd enrichment culture, container is placed in 25 DEG C of constant-temperature tables shaking culture 3 days under the rotating speed of 160 revs/min, obtains phosphorus ore pit water microorganism species enrichment culture liquid (namely so repeatedly inoculating enrichment culture 3 times).
2) phosphorus ore pit water microorganism species enrichment culture liquid dissolves mid low grade phosphate rock: add in container by without phosphorus substratum and mid low grade phosphate rock, add phosphorus ore pit water microorganism species enrichment culture liquid again to mix, container is placed in 22 DEG C of constant-temperature tables afterwards, under 140 revs/min of rotating speeds, shaking culture obtains titanium pigment in 9 days.Wherein the volume ratio of without phosphorus substratum and phosphorus ore pit water microorganism species enrichment culture liquid is 1:0.2, and the without phosphorus substratum of every 1000ml adds 15g mid low grade phosphate rock.
In the mid low grade phosphate rock that the present embodiment adopts, the mass content of Vanadium Pentoxide in FLAKES is 22.8%, and molten phosphorus rate reaches 75.4%.
Embodiment 5
Utilize phosphorus ore pit water microorganism species to dissolve a method for mid low grade phosphate rock, comprise the steps:
1) enrichment culture of phosphorus ore pit water microorganism species: will have phosphorus substratum and phosphorus ore pit water by volume 1:0.7 load in container (as triangular flask), container is placed in 22 DEG C of constant-temperature tables shaking culture 5 days under the rotating speed of 120 revs/min, obtains the phosphorus ore pit water microorganism species enrichment culture liquid A of the 1st enrichment culture.
To have in the phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.8 loading by volume container of phosphorus substratum and the 1st enrichment culture, container is placed in 25 DEG C of constant-temperature tables shaking culture 3 days under the rotating speed of 160 revs/min, obtains the phosphorus ore pit water microorganism species enrichment culture liquid A of the 2nd enrichment culture.
To have in the phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.6 loading by volume container of phosphorus substratum and the 2nd enrichment culture, container is placed in 25 DEG C of constant-temperature tables shaking culture 4 days under the rotating speed of 140 revs/min, obtains the phosphorus ore pit water microorganism species enrichment culture liquid A of the 3rd enrichment culture.
To have in the phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.6 loading by volume container of phosphorus substratum and the 3rd enrichment culture, container is placed in 25 DEG C of constant-temperature tables shaking culture 4 days under the rotating speed of 120 revs/min, obtains the phosphorus ore pit water microorganism species enrichment culture liquid A of the 4th enrichment culture.
To have in the phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.5 loading by volume container of phosphorus substratum and the 4th enrichment culture, container is placed in 28 DEG C of constant-temperature tables shaking culture 4 days under the rotating speed of 150 revs/min, obtains phosphorus ore pit water microorganism species enrichment culture liquid (namely so repeatedly inoculating enrichment culture 5 times).
2) phosphorus ore pit water microorganism species enrichment culture liquid dissolves mid low grade phosphate rock: add in container by without phosphorus substratum and mid low grade phosphate rock, add phosphorus ore pit water microorganism species enrichment culture liquid again to mix, container is placed in 30 DEG C of constant-temperature tables afterwards, under 120 revs/min of rotating speeds, shaking culture obtains titanium pigment in 7 days.Wherein the volume ratio of without phosphorus substratum and phosphorus ore pit water microorganism species enrichment culture liquid is 1:0.25, and the without phosphorus substratum of every 1000ml adds 14g mid low grade phosphate rock.
In the mid low grade phosphate rock that the present embodiment adopts, the mass content of Vanadium Pentoxide in FLAKES is 25.1%, and molten phosphorus rate reaches 64.9%.
The bound of each raw material cited by the present invention, interval value, and the bound of processing parameter (as temperature, time etc.), interval value can realize the present invention, do not enumerate embodiment at this.
Claims (7)
1. the method utilizing phosphorus ore pit water microorganism species to dissolve mid low grade phosphate rock, it is characterized in that comprising the steps: 1) enrichment culture of phosphorus ore pit water microorganism species: phosphorus ore pit water microorganism species is carried out enrichment culture, obtains phosphorus ore pit water microorganism species enrichment culture liquid; 2) phosphorus ore pit water microorganism species enrichment culture liquid dissolves mid low grade phosphate rock: without phosphorus substratum and mid low grade phosphate rock are added in container, then adds phosphorus ore pit water microorganism species enrichment culture liquid and cultivate.
2. a kind of method utilizing phosphorus ore pit water microorganism species to dissolve mid low grade phosphate rock according to claim 1, it is characterized in that: step 1) enrichment culture of described phosphorus ore pit water microorganism species comprise a will have phosphorus substratum and phosphorus ore pit water by volume 1:0.5-0.8 load in container, container is placed in constant-temperature table shaking culture, obtains phosphorus ore pit water microorganism species enrichment culture liquid A; B will have in phosphorus substratum and phosphorus ore pit water microorganism species enrichment culture liquid A 1:0.5-0.8 loading by volume container, container will be placed in constant-temperature table shaking culture, obtain the phosphorus ore pit water microorganism species enrichment culture liquid A of enrichment again; C repeating step b1-3 time, obtains phosphorus ore pit water microorganism species enrichment culture liquid.
3. a kind of method utilizing phosphorus ore pit water microorganism species to dissolve mid low grade phosphate rock according to claim 2, it is characterized in that: constant-temperature table temperature is 22-30 DEG C, rotating speed is 100-160 rev/min, and the shaking culture time is 3-5 days.
4. a kind of method utilizing phosphorus ore pit water microorganism species to dissolve mid low grade phosphate rock according to claim 1, it is characterized in that: step 2) described phosphorus ore pit water microorganism species enrichment culture liquid dissolve mid low grade phosphate rock comprise by without phosphorus substratum and phosphorus ore pit water microorganism species enrichment culture liquid by volume 1:0.2-0.3 load in container, 10-20g mid low grade phosphate rock is added again by the without phosphorus substratum of every 1000ml, container is placed in 22-30 DEG C of constant-temperature table after mixing, shaking culture 7-10 days under 120-160 rev/min of rotating speed.
5. a kind of method utilizing phosphorus ore pit water microorganism species to dissolve mid low grade phosphate rock according to claim 1 or 4, is characterized in that: described without phosphorus substratum consists of 10g/L glucose, 0.5g/L yeast extract, 0.5g/L (NH
4)
2sO
4, 0.2g/LKCl, 0.1g/LMgSO
47H
2o, 0.0001g/LMnSO
4h
2o, 0.0001g/LFeSO
47H
2o, solvent is sterilized water.
6. a kind of phosphorus ore pit water microorganism species that utilizes according to claim 2 dissolves the method for mid low grade phosphate rock, it is characterized in that: described in have phosphorus substratum to consist of 10g/L glucose, 0.5g/L yeast extract, 0.5g/L (NH
4)
2sO
4, 0.2g/LKCl, 0.1g/LMgSO
47H
2o, 0.0001g/LMnSO
4h
2o, 0.0001g/LFeSO
47H
2the calcium phosphate of O, 10-20g/L, solvent is sterilized water.
7. a kind of method utilizing phosphorus ore pit water microorganism species to dissolve mid low grade phosphate rock according to claim 1, it is characterized in that: in described mid low grade phosphate rock, the mass content of Vanadium Pentoxide in FLAKES is lower than 30%, described mid low grade phosphate rock needs to be crushed to particle diameter for 50-200 order before using.
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CN109321558A (en) * | 2018-10-31 | 2019-02-12 | 武汉工程大学 | The method for preparing phosphate solubilizing microorganism sustained release sodium alginate micro ball using emulsion process |
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CN108753615A (en) * | 2018-05-24 | 2018-11-06 | 江口县旭辉生态农业科技有限公司 | A method of dissolving low grade rock phosphate using Haloragidaceae Myriophyllum spicatum endophyte |
CN109321558A (en) * | 2018-10-31 | 2019-02-12 | 武汉工程大学 | The method for preparing phosphate solubilizing microorganism sustained release sodium alginate micro ball using emulsion process |
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