CN106978183A - Preparation method of acid-activated palygorskite-based soil heavy metal passivation material - Google Patents
Preparation method of acid-activated palygorskite-based soil heavy metal passivation material Download PDFInfo
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- CN106978183A CN106978183A CN201710200077.7A CN201710200077A CN106978183A CN 106978183 A CN106978183 A CN 106978183A CN 201710200077 A CN201710200077 A CN 201710200077A CN 106978183 A CN106978183 A CN 106978183A
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- palygorskite
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- sulfuric acid
- clay
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- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 92
- 239000002689 soil Substances 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910001385 heavy metal Inorganic materials 0.000 title abstract description 17
- 239000002253 acid Substances 0.000 title abstract description 7
- 238000002161 passivation Methods 0.000 title abstract description 7
- 239000004927 clay Substances 0.000 claims abstract description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 62
- 238000002156 mixing Methods 0.000 claims description 18
- 239000002585 base Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 238000007873 sieving Methods 0.000 claims description 13
- 239000013049 sediment Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 6
- 239000011707 mineral Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract description 2
- 239000002734 clay mineral Substances 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 231100001240 inorganic pollutant Toxicity 0.000 abstract 1
- 238000005342 ion exchange Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000002680 soil gas Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/04—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only applied in a physical form other than a solution or a grout, e.g. as granules or gases
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the technical field of environment-friendly materials and preparation thereof, in particular to a preparation method of an acid-activated palygorskite-based soil heavy metal passivation material. The palygorskite clay is used as a non-metallic clay mineral widely applied to the restoration of heavy metal polluted soil at present, is rich in mineral resources in China and low in price, has the function of adsorbing harmful and various organic and inorganic pollutants, does not produce secondary pollution, and has incomparable advantages of other non-metallic minerals. The acidified palygorskite clay has no impurity, dispersed crystal beam, gradually dissolved octahedral cation and expanded microporous pore passage, and thus has raised specific surface area, raised adsorption performance and ion exchange capacity, and thus higher application value and economic value.
Description
Technical field
The present invention relates to environment-friendly materials and its preparing technical field, particularly a kind of Palygorskite base heavy metal-polluted soil
The preparation method of passivating material.
Background technology
Soil is Main Natural Resources for the survival of mankind, is also the important component of human ecological environment.With
The pollution of heavy metal is increasingly serious in the fast development of industrial or agricultural, soil-plant-environmental system.
Heavy metal contaminated soil remediation technology is studied and demonstrated for China, and has started to heavy-metal contaminated soil
The implementation of recovery project, major technique includes barrier landfill, curing/stabilizing, phytoremediation, soil cleaning, Thermal desorption and electricity
It is dynamic to repair.Wherein first three technology has successful Engineering Projects at home, and soil cleaning and mercury contaminated soil Thermal desorption have entered
Row engineering mimoir, electro reclamation is at present also in the laboratory research stage.
In recent years, for the reparation of mild or moderate contaminated soil, the research of in-situ passivation technology has largely been carried out.Heavy metal is former
Position passivating technique is a kind of restorative procedure of contaminated soil, points to contaminated soil and adds some active materials, to reduce heavy metal
Valid density in soil changes its redox state, so as to effectively reduce its migration, toxicity and biological effectiveness.
Wide variety of in heavy-metal contaminated soil reparation at present is non-metal clay mineral, such as bentonite, sepiolite, zeolite.
But existing palygorskite base heavy metal passivating material is only crushing, mixing, and simply directly dispensing is used after modification, palygorskite
Practical effect is limited, needs to continue to increase palygorskite consumption to reach that purpose is repaired in soil pollution, causes palygorskite
Waste and consumption is increased.
The content of the invention
It is an object of the invention to provide the Palygorskite base soil huge sum of money that a kind of utilization rate height, modified effect are protruded
Belong to the preparation method of passivating material.
The technical solution adopted for the present invention to solve the technical problems is as follows：
A kind of preparation method of Palygorskite base heavy metal-polluted soil passivating material, is comprised the following steps：
A, dry naturally
Palygorskite ore is dried 3-7 days in the sunlight, prevents rainwater from soaking palygorskite；
B, broken sieving
Palygorskite ore is broken into palygorskite clay, sieve aperture 150-200 mesh is filtered in palygorskite clay sieving；
C, alkali chelating
Palygorskite clay is mixed with sulfuric acid solution, stirring is well mixed it；
D, precipitation dries pulverizing
Mixed liquor is staticly settled, and is dried sediment and is crushed, finished product.
Palygorskite clay presses solid-to-liquid ratio 1 with sulfuric acid solution in the step C：10 mixing, sulfuric acid solution mass concentration 2.5 ~
12 ~ 108h is stirred under conditions of 20%, the r/min of low whipping speed 500, it is well mixed.
Palygorskite clay presses solid-to-liquid ratio 1 with sulfuric acid solution in the step C：10 mixing, sulfuric acid solution mass concentration 2.5 ~
72h is stirred under conditions of 20%, the r/min of low whipping speed 500, it is well mixed.
Palygorskite clay presses solid-to-liquid ratio 1 with sulfuric acid solution in the step C：10 mixing, sulfuric acid solution mass concentration
72h is stirred under conditions of 12.5%, the r/min of low whipping speed 500, it is well mixed.
Sediment is dried at 70 DEG C in the step D.
Beneficial effects of the present invention are：
1st, palygorskite ore is dried 3-7 days in the sunlight, not by the way of heating, drying and prevents rainwater from soaking palygorskite；First
Broken sieving is carried out after daylight is dried, the chemical substance being effectively ensured in palygorskite ore is stable.In addition dried in the air by daylight
Shine control mineral surface humidity and be easy to follow-up crush.
2nd, palygorskite clay and sulfuric acid solution press solid-to-liquid ratio 1 in the step C：10 mixing, sulfuric acid solution mass concentration 2.5
~20%.Within the above range, the passivation effect of such a passivating material can increase with the increase of sulfuric acid solution mass concentration, but such as
Fruit sulfuric acid solution mass concentration is too high, can change the pH value of soil, influences the normal growth of plant, and research shows, sulphur
Sour solvent content is minimum during acid solution mass concentration 12.5%.
3rd, sediment is dried at 70 DEG C, gets through the inner passage of palygorskite, exposes more inner surfaces and active group
Group.High temperature drying effectively control end properties are avoided, batch production quality is more easy to control.Palygorskite clay have absorption harmful and
The function of various organic and inorganic pollution, it is saturating that palygorskite clay can not only break soil hardening, chesson, raising soil
Gas, the reduction soil weight, promote soil microbial activities, enhancing soil fertility penetration, moreover it is possible to improved soil, administer waste
Desert, water conservation drought resisting strengthens crops antibacterial ability, crop yield is improved, while secondary pollution will not be produced.
Palygorskite clay is used as the wide variety of nonmetallic clay in heavy-metal contaminated soil reparation at present in summary
Mineral, it is abundant in Mineral Resources in China, cheap, and palygorskite clay has absorption harmful and various organic and inorganic dirt
The function of thing is contaminated, while secondary pollution will not be produced, has the advantages that other nonmetallic minerals are incomparable.It is acidified processing with
Palygorskite clay afterwards, eliminates the impurity in palygorskite clay, and the brilliant beam of state of aggregation is also disperseed, and octahedral cations are gradually
Dissolving, micropore canals expand, reached purifying palygorskite clay purpose, improve its specific surface area, to absorption property and from
Sub- exchange capacity has facilitation, so that the palygorskite clay after being acidified has more application value than untreated palygorskite clay
And economic value.
Brief description of the drawings
Fig. 1 influences schematic diagram I for the present invention on the sour solvent content of palygorskite ore；
Fig. 2 influences schematic diagram II for the present invention on the sour solvent content of palygorskite ore.
Embodiment
A kind of preparation method of Palygorskite base heavy metal-polluted soil passivating material, is comprised the following steps：
A, dry naturally
Palygorskite ore is dried 3-7 days in the sunlight, prevents rainwater from soaking palygorskite；
B, broken sieving
Palygorskite ore is broken into palygorskite clay, sieve aperture 150-200 mesh is filtered in palygorskite clay sieving；
C, alkali chelating
Palygorskite clay is mixed with sulfuric acid solution, stirring is well mixed it；
D, precipitation dries pulverizing
Mixed liquor is staticly settled, and is dried sediment and is crushed, finished product.
It is preferred that the step C in palygorskite clay and sulfuric acid solution press solid-to-liquid ratio 1：10 mixing, sulfuric acid solution quality is dense
12 ~ 108h is stirred under conditions of degree 2.5 ~ 20%, the r/min of low whipping speed 500, it is well mixed.
It is preferred that the step C in palygorskite clay and sulfuric acid solution press solid-to-liquid ratio 1：10 mixing, sulfuric acid solution quality is dense
72h is stirred under conditions of degree 2.5 ~ 20%, the r/min of low whipping speed 500, it is well mixed.
It is preferred that the step C in palygorskite clay and sulfuric acid solution press solid-to-liquid ratio 1：10 mixing, sulfuric acid solution quality is dense
72h is stirred under conditions of degree 12.5%, the r/min of low whipping speed 500, it is well mixed.
It is preferred that the step D in sediment dried at 70 DEG C.
Middle palygorskite ore in the embodiment 1 to 3 selects the palygorskite ore that Linze county is exploited.Other ground panelings
Palygorskite ore can also be used for this case.
Embodiment 1
A kind of preparation method of Palygorskite base heavy metal-polluted soil passivating material, is comprised the following steps：
A, dry naturally
Palygorskite ore is dried 3-7 days in the sunlight, prevents rainwater from soaking palygorskite；
B, broken sieving
Palygorskite ore is broken into palygorskite clay, sieve aperture 150-200 mesh is filtered in palygorskite clay sieving；
C, alkali chelating
Palygorskite clay presses solid-to-liquid ratio 1 with sulfuric acid solution：10 mixing, sulfuric acid solution mass concentration 2.5 ~ 20%, low whipping speed
12 ~ 108h is stirred under conditions of 500 r/min, it is well mixed；
D, precipitation dries pulverizing
Mixed liquor is staticly settled, and sediment is dried at 70 DEG C and is crushed, finished product.
Embodiment 2
A kind of preparation method of Palygorskite base heavy metal-polluted soil passivating material, is comprised the following steps：
A, dry naturally
Palygorskite ore is dried 3-7 days in the sunlight, prevents rainwater from soaking palygorskite；
B, broken sieving
Palygorskite ore is broken into palygorskite clay, sieve aperture 150-200 mesh is filtered in palygorskite clay sieving；
C, alkali chelating
Palygorskite clay presses solid-to-liquid ratio 1 with sulfuric acid solution：10 mixing, sulfuric acid solution mass concentration 2.5 ~ 20%, low whipping speed
72h is stirred under conditions of 500 r/min, it is well mixed；
D, precipitation dries pulverizing
Mixed liquor is staticly settled, and sediment is dried at 70 DEG C and is crushed, finished product.
Embodiment 3
A kind of preparation method of Palygorskite base heavy metal-polluted soil passivating material, is comprised the following steps：
A, dry naturally
Palygorskite ore is dried 3-7 days in the sunlight, prevents rainwater from soaking palygorskite；
B, broken sieving
Palygorskite ore is broken into palygorskite clay, sieve aperture 150-200 mesh is filtered in palygorskite clay sieving；
C, alkali chelating
Palygorskite clay presses solid-to-liquid ratio 1 with sulfuric acid solution：10 mixing, sulfuric acid solution mass concentration 12.5%, low whipping speed 500
72h is stirred under conditions of r/min, it is well mixed；
D, precipitation dries pulverizing
Mixed liquor is staticly settled, and sediment is dried at 70 DEG C and is crushed, finished product.
Contrast test
It is 1 in solid-to-liquid ratio：10th, under conditions of mixing speed is 500 r/min, the palygorskite powder of 150 mesh is dispersed in respectively
Mass fraction is 2.5%, 5%, 7.5%, 10%, 12.5%, 15%, 20% H2SO4Acid is carried out in solution, after stirring modified, point
Not in after acid activation 12h, 24h, 36h, 48h, 72h, 96h and 108h, progress staticly settles drying（70 DEG C of drying temperature）Afterwards
To solid product, by Mechanical Crushing and sub-sieve, sour 49 kinds of the modified attapulgite base passivator of 10 mesh is prepared.Difference compound concentration
The Ni contaminated soils for being 400mg/kg for 800mg/kg Cu, Cr, Zn contaminated soil and concentration, are sufficiently stirred for mixing, as people
Work heavy metal pollution soil sample.With addition of the 49 kinds of concave convex rod passivator prepared by 16g/kg, 4 kinds of artificial heavy metals are added
Soil sample is polluted, is sufficiently stirred for mixing, keeps field capacity to carry out after soaking passivation 30 days with deionized water, dries soil sample, survey
Determine heavy metal DTPA extraction state contents.Measurement result See Figure：
Different types of Palygorskite difference heavy metal Cu, Cr, Zn, Ni pollution soil sample Passivation Treatment, heavy as shown in Figure 1
Ni metal, Cr, Zn, Ni available state concentration are with acid treatment H2SO4The change of percentage composition is generally in becoming for rising after falling before
Gesture.The optimal palygorskite acid activation H of the heavy metal-passivated pollution soil sample of Palygorskite2SO4Percentage composition is 12.5%.
As shown in Figure 2 at different types of sour modified attapulgite difference heavy metal Cu, Cr, Zn, Ni pollution soil sample passivation
Reason, heavy metal Cu, Cr, Zn, Ni available state concentration with the change of acid treatment time generally in the trend risen after falling before but
Change is not obvious.The optimal palygorskite acid activation time of the heavy metal-passivated pollution soil sample of Palygorskite is 72h.
Claims (5)
1. a kind of preparation method of Palygorskite base heavy metal-polluted soil passivating material, it is characterised in that comprise the following steps：
A, dry naturally
Palygorskite ore is dried 3-7 days in the sunlight, prevents rainwater from soaking palygorskite；
B, broken sieving
Palygorskite ore is broken into palygorskite clay, sieve aperture 150-200 mesh is filtered in palygorskite clay sieving；
C, alkali chelating
Palygorskite clay is mixed with sulfuric acid solution, stirring is well mixed it；
D, precipitation dries pulverizing
Mixed liquor is staticly settled, and is dried sediment and is crushed, finished product.
2. a kind of preparation method of Palygorskite base heavy metal-polluted soil passivating material, its feature according to claim 1
It is that palygorskite clay and sulfuric acid solution are by solid-to-liquid ratio 1 in the step C：10 mixing, sulfuric acid solution mass concentration 2.5 ~ 20%,
12 ~ 108h is stirred under conditions of the r/min of low whipping speed 500, it is well mixed.
3. a kind of preparation method of Palygorskite base heavy metal-polluted soil passivating material, its feature according to claim 1
It is that palygorskite clay and sulfuric acid solution are by solid-to-liquid ratio 1 in the step C：10 mixing, sulfuric acid solution mass concentration 2.5 ~ 20%,
72h is stirred under conditions of the r/min of low whipping speed 500, it is well mixed.
4. a kind of preparation method of Palygorskite base heavy metal-polluted soil passivating material, its feature according to claim 3
It is that palygorskite clay and sulfuric acid solution are by solid-to-liquid ratio 1 in the step C：10 mixing, sulfuric acid solution mass concentration 12.5%,
72h is stirred under conditions of the r/min of mixing speed 500, it is well mixed.
5. a kind of preparation method of Palygorskite base heavy metal-polluted soil passivating material, its feature according to claim 1
It is in the step D that sediment is dried at 70 DEG C.
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| CN108586128A (en) * | 2018-05-03 | 2018-09-28 | 新疆泰谷生物肥料有限公司 | A kind of preparation method of slowly releasing trace element fertilizer |
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| CN107308906A (en) * | 2017-08-21 | 2017-11-03 | 苏州中晟环境修复股份有限公司 | A kind of clay mineral sorbing material of restoration of soil polluted by heavy metal and preparation method thereof |
| CN108586128A (en) * | 2018-05-03 | 2018-09-28 | 新疆泰谷生物肥料有限公司 | A kind of preparation method of slowly releasing trace element fertilizer |
| CN108586128B (en) * | 2018-05-03 | 2021-08-24 | 湖南重金属污染耕地安全高效利用工程研究中心有限公司 | Preparation method of slow-release trace element fertilizer |
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