CN112457861A - Method and device for preparing phosphogypsum soil conditioner - Google Patents
Method and device for preparing phosphogypsum soil conditioner Download PDFInfo
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- CN112457861A CN112457861A CN202011414156.6A CN202011414156A CN112457861A CN 112457861 A CN112457861 A CN 112457861A CN 202011414156 A CN202011414156 A CN 202011414156A CN 112457861 A CN112457861 A CN 112457861A
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- phosphogypsum
- silica gel
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- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000003516 soil conditioner Substances 0.000 title claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229920001661 Chitosan Polymers 0.000 claims abstract description 54
- 239000002689 soil Substances 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 27
- 239000000835 fiber Substances 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 20
- 238000000855 fermentation Methods 0.000 claims abstract description 18
- 230000004151 fermentation Effects 0.000 claims abstract description 18
- 235000019738 Limestone Nutrition 0.000 claims abstract description 16
- 239000006028 limestone Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 230000000813 microbial effect Effects 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000002028 Biomass Substances 0.000 claims abstract description 8
- 239000000741 silica gel Substances 0.000 claims description 37
- 229910002027 silica gel Inorganic materials 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 230000008878 coupling Effects 0.000 claims description 10
- 238000010168 coupling process Methods 0.000 claims description 10
- 238000005859 coupling reaction Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000000053 physical method Methods 0.000 claims description 4
- 241000609240 Ambelania acida Species 0.000 claims description 3
- 241000194107 Bacillus megaterium Species 0.000 claims description 3
- 244000063299 Bacillus subtilis Species 0.000 claims description 3
- 235000014469 Bacillus subtilis Nutrition 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 241000235342 Saccharomycetes Species 0.000 claims description 3
- 239000010905 bagasse Substances 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 239000010902 straw Substances 0.000 claims description 3
- 241000194108 Bacillus licheniformis Species 0.000 claims description 2
- 241000894006 Bacteria Species 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241000193417 Brevibacillus laterosporus Species 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 241000187395 Streptomyces microflavus Species 0.000 claims description 2
- 241000223260 Trichoderma harzianum Species 0.000 claims description 2
- 229920002522 Wood fibre Polymers 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- 229940107666 astragalus root Drugs 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 235000015099 wheat brans Nutrition 0.000 claims description 2
- 239000002025 wood fiber Substances 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000004071 biological effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000006872 improvement Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 244000061456 Solanum tuberosum Species 0.000 description 4
- 235000002595 Solanum tuberosum Nutrition 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 235000012015 potatoes Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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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
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (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)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method and a device for preparing a phosphogypsum soil conditioner, wherein the method comprises the following steps: crushing the phosphogypsum, removing impurities, and removing organic matters and soluble impurities in the phosphogypsum to obtain phosphogypsum powder; taking biomass fibers doped with a microbial agent, fermenting, mixing a fermentation product with phosphogypsum powder, and simultaneously adding limestone and chitosan modified silica gel to obtain a mixture; and stirring the mixture, and drying to obtain the catalyst. The device comprises a crushing module, an impurity removal module, a fermentation module, a mixing module and a drying module. The soil conditioner takes the phosphogypsum as the main material, realizes the resource utilization of the phosphogypsum and avoids the environment pollution after the phosphogypsum is discarded; the soil conditioner is simultaneously added with limestone, microbial agent and chitosan modified silica gel, so that the physical, chemical and biological properties of soil can be improved, the activity of heavy metal ions is reduced, and the heavy metal ions are firmly fixed in the soil, thereby reducing the absorption of crops to the heavy metal ions in the soil.
Description
Technical Field
The invention relates to the technical field of soil improvement, in particular to a method and a device for preparing a phosphogypsum soil conditioner.
Background
The phosphogypsum mainly has two kinds of gray black and gray white, the particle diameter is generally 5-50 mu m, and the content of crystal water is 20-25%. Phosphogypsum is a solid waste produced in a wet-process phosphoric acid process, and the components of the phosphogypsum are mainly calcium sulfate dihydrate. The composition of the phosphogypsum is complex, besides calcium sulfate, incompletely decomposed phosphorite, residual phosphoric acid, fluoride, acid insoluble substances, organic matters and the like exist, and the existence of fluorine and the organic matters has the greatest influence on the resource utilization of the phosphogypsum. The random discharge and accumulation of the phosphogypsum seriously damage the ecological environment, not only pollutes underground water resources, but also causes the waste of land resources. The phosphogypsum contains CaO, MgO and SO2、Al2O3、Fe2O3、SiO2、P2O5And the reasonable utilization of the substances can generate higher value.
The heavy metal pollution of soil (referred to as soil heavy metal pollution) refers to the condition that the content of trace metal elements in soil exceeds the background value and is excessively high due to excessive deposition because of human activities. The soil heavy metal is a phenomenon that the heavy metal in the soil is obviously higher than the original content and causes the deterioration of the quality of the ecological environment because the metal is added into the soil due to the activity of human beings. The heavy metal is a metal having a specific gravity of 5.0 or more, such as Fe, Mn, Zn, Cd, Hg, Ni, Co, etc. Because of their high iron and manganese content, soils are generally considered to be not soil polluting elements, but the toxicity caused by iron and manganese is also of sufficient importance under strongly reducing conditions. The heavy metal pollution sources of soil mainly include: the method comprises the following steps of influencing the background content of heavy metals in soil by the weathering process of the parent soil, carrying natural physical and chemical migration processes by wind power and water power, additionally inputting heavy metals in soil by industrial production of different industrial and mining enterprises, inputting heavy metals in soil under the influence of agricultural production activities, and introducing heavy metal pollution to soil by transportation.
Disclosure of Invention
The invention aims to provide a method and a device for preparing a phosphogypsum soil conditioner, which are used for preparing a soil pond conditioner by taking phosphogypsum as a basic substance and can effectively solve the problem of heavy metal pollution of soil.
The invention realizes the purpose through the following technical scheme:
a method for preparing a phosphogypsum soil conditioner is characterized by comprising the following steps: comprises the steps of
The method comprises the following steps: firstly crushing the phosphogypsum, and then removing impurities to remove organic matters and soluble impurities in the phosphogypsum to obtain phosphogypsum powder;
step two: selecting biomass fibers doped with a microbial agent, fermenting, mixing a fermentation product with the phosphogypsum powder, and simultaneously adding limestone and chitosan modified silica gel to obtain a mixture;
step three: and stirring the mixture, and drying to obtain the phosphogypsum soil conditioner.
The further improvement is that the impurity removal treatment adopts one or the combination of a chemical method, a physical method or a heat treatment method.
The further improvement is that the microbial agent is one or more of saccharomycetes, bacillus subtilis, bacillus licheniformis, astragalus root nodule bacteria, bacillus laterosporus, bacillus megaterium, trichoderma harzianum or streptomyces microflavus;
the biomass fiber is selected from one or more of straw fiber, bamboo fiber, wood fiber, bagasse fiber, rice hull fiber and wheat bran fiber.
The further improvement is that the stirring treatment refers to stirring for 2-10h at the rotating speed of 500-1200 r/min.
The further improvement is that the preparation method of the chitosan modified silica gel comprises the following steps:
(1) selecting silica gel particles with the particle size of 0.1-0.5 mu m, soaking the silica gel particles in 2-6mol/L phosphoric acid for 12-18h, washing the silica gel particles to be neutral by deionized water, and drying the silica gel particles at 80-120 ℃ to constant weight to obtain a silica gel matrix for later use;
(2) mixing N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and 60-80 vt% ethanol solution according to the proportion of 1g:15-20mL, stirring until the N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane is completely dissolved, and standing for 8-20h to obtain a coupling solution for later use;
(3) mixing chitosan and low molecular alcohol according to the proportion of 1g:30-50mL, adding an activating agent accounting for 0.5-2% of the total volume of the system, and performing ultrasonic dispersion for 3-5min to obtain a chitosan modified solution for later use;
(4) and mixing the silica gel matrix, the coupling solution and the chitosan modified solution, heating and refluxing for 4-8h at 75-85 ℃, and washing and drying after solid-liquid separation to obtain the chitosan modified silica gel.
The further improvement is that the low molecular alcohol is one of methanol, ethanol or isopropanol.
In a further improvement, the washing and drying refer to: washing with deionized water, washing with acetone solution, and drying at room temperature.
In a further improvement, the activator is a zinc or nickel salt.
The further improvement is that the mass ratio of the fermentation product, the phosphogypsum powder, the limestone and the chitosan modified silica gel is 1:5-10:2-4: 0.5-1.5.
An apparatus for implementing the above method, the apparatus comprising:
the crushing module is used for crushing the phosphogypsum;
the impurity removal module is used for removing impurities from the crushed phosphogypsum;
the fermentation module is used for fermenting the biomass fibers doped with the microbial agent;
the mixing module is used for mixing the fermentation product with the phosphogypsum powder, the limestone and the chitosan modified silica gel and stirring the mixture;
and the drying module is used for drying the mixture after stirring treatment.
The chitosan modified silica gel utilizes the adsorption performance of the silica gel and the selective performance of chitosan, and is chemically bonded into a whole by N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, so that the obtained chitosan modified silica gel can specifically adsorb heavy metal ions, and meanwhile, the polymer has stronger biocompatibility and higher stability in a complex soil environment through chemical bonding, and the adsorption quantity and the adsorption rate of the polymer to the heavy metal ions are improved.
The invention has the beneficial effects that: the soil conditioner takes the phosphogypsum as the main material, realizes the resource utilization of the phosphogypsum and avoids the environment pollution after the phosphogypsum is discarded; the soil conditioner is simultaneously added with limestone, microbial agent and chitosan modified silica gel, so that the physical, chemical and biological properties of soil can be effectively improved, the activity of heavy metal ions is reduced, and the heavy metal ions are firmly fixed in the soil, thereby reducing the absorption of crops to the heavy metal ions in the soil.
Drawings
FIG. 1 is a schematic diagram of the present invention.
Detailed Description
The present application will now be described in further detail with reference to the drawings, it should be noted that the following detailed description is given for illustrative purposes only and is not to be construed as limiting the scope of the present application, as those skilled in the art will be able to make numerous insubstantial modifications and adaptations to the present application based on the above disclosure.
Example 1
As shown in fig. 1, a method for preparing a phosphogypsum soil conditioner comprises the following steps:
the method comprises the following steps: firstly crushing the phosphogypsum, then removing impurities by a water washing physical method, removing organic matters and soluble impurities in the phosphogypsum, and obtaining the phosphogypsum powder.
Step two: selecting straw fiber doped with saccharomycetes, fermenting (fermenting at 60 ℃ for 12 days, the same below), mixing a fermentation product with the phosphogypsum powder, and simultaneously adding limestone and chitosan modified silica gel to obtain a mixture, wherein the mass ratio of the fermentation product to the phosphogypsum powder to the limestone to the chitosan modified silica gel is 1:5:2: 0.5.
The preparation method of the chitosan modified silica gel comprises the following steps:
(1) selecting silica gel particles with the particle size of 0.1 mu m, soaking the silica gel particles in 2mol/L phosphoric acid for 18h, washing the silica gel particles to be neutral by using deionized water, and drying the silica gel particles at 80 ℃ to constant weight to obtain a silica gel matrix for later use;
(2) mixing N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane with 60 vt% ethanol solution according to the proportion of 1g:20mL, stirring until the N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane is completely dissolved, and standing for 8 hours to obtain a coupling solution for later use;
(3) mixing chitosan and methanol according to the proportion of 1g:30mL, adding zinc chloride accounting for 0.5% of the total volume of the system, and performing ultrasonic dispersion for 3min to obtain a chitosan modified solution for later use;
(4) and mixing the silica gel matrix, the coupling solution and the chitosan modified solution, heating and refluxing for 8 hours at 75 ℃, after solid-liquid separation, washing with deionized water, washing with an acetone solution, and finally drying at room temperature to obtain the chitosan modified silica gel.
Step three: stirring the mixture for 10h at the rotating speed of 500r/min, and drying to obtain the phosphogypsum soil conditioner.
Example 2
A method for preparing a phosphogypsum soil conditioner comprises the following steps:
the method comprises the following steps: firstly crushing the phosphogypsum, and then removing impurities by a flotation physical method to remove organic matters and soluble impurities in the phosphogypsum to obtain phosphogypsum powder.
Step two: selecting bagasse fibers doped with bacillus subtilis, fermenting, mixing a fermentation product with the phosphogypsum powder, and simultaneously adding limestone and chitosan modified silica gel to obtain a mixture, wherein the mass ratio of the fermentation product to the phosphogypsum powder to the limestone to the chitosan modified silica gel is 1:8:3: 1.
The preparation method of the chitosan modified silica gel comprises the following steps:
(1) selecting silica gel particles with the particle size of 0.3 mu m, soaking the silica gel particles in 4mol/L phosphoric acid for 15h, washing the silica gel particles to be neutral by using deionized water, and drying the silica gel particles at 100 ℃ to constant weight to obtain a silica gel matrix for later use;
(2) mixing N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and 70 vt% ethanol solution according to the proportion of 1g to 18mL, stirring until the N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane is completely dissolved, and standing for 14h to obtain a coupling solution for later use;
(3) mixing chitosan and ethanol according to the proportion of 1g to 40mL, adding zinc chloride accounting for 1% of the total volume of the system, and performing ultrasonic dispersion for 4min to obtain a chitosan modified solution for later use;
(4) and mixing the silica gel matrix, the coupling solution and the chitosan modified solution, heating and refluxing for 6h at 80 ℃, after solid-liquid separation, washing with deionized water, washing with an acetone solution, and finally drying at room temperature to obtain the chitosan modified silica gel.
Step three: and stirring the mixture for 6 hours at the rotating speed of 800r/min, and drying to obtain the phosphogypsum soil conditioner.
Example 3
A method for preparing a phosphogypsum soil conditioner comprises the following steps:
the method comprises the following steps: firstly crushing the phosphogypsum, then removing impurities by a thermal treatment method, removing organic matters and soluble impurities in the phosphogypsum, and obtaining phosphogypsum powder.
Step two: selecting rice hull fiber doped with bacillus megatherium, fermenting, mixing a fermentation product with the phosphogypsum powder, and simultaneously adding limestone and chitosan modified silica gel to obtain a mixture, wherein the mass ratio of the fermentation product to the phosphogypsum powder to the limestone to the chitosan modified silica gel is 1:10:4: 1.5.
The preparation method of the chitosan modified silica gel comprises the following steps:
(1) selecting silica gel particles with the particle size of 0.5 mu m, soaking the silica gel particles in 6mol/L phosphoric acid for 12h, washing the silica gel particles to be neutral by using deionized water, and drying the silica gel particles at 120 ℃ to constant weight to obtain a silica gel matrix for later use;
(2) mixing N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and 80 vt% ethanol solution according to the proportion of 1g:15mL, stirring until the N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane is completely dissolved, and standing for 20 hours to obtain a coupling solution for later use;
(3) mixing chitosan and isopropanol according to the proportion of 1g:50mL, adding nickel chloride accounting for 0.5% of the total volume of the system, and performing ultrasonic dispersion for 5min to obtain a chitosan modified solution for later use;
(4) and mixing the silica gel matrix, the coupling solution and the chitosan modified solution, heating and refluxing for 4 hours at 85 ℃, after solid-liquid separation, washing with deionized water, washing with an acetone solution, and finally drying at room temperature to obtain the chitosan modified silica gel.
Step three: and stirring the mixture for 2 hours at the rotating speed of 1200r/min, and drying to obtain the phosphogypsum soil conditioner.
Comparative example 1
A method for preparing a phosphogypsum soil conditioner, which has the basically same steps as the example 2, and the only difference is that: the chitosan modified silica gel is replaced by chitosan with equal mass.
Comparative example 2
A method for preparing a phosphogypsum soil conditioner, which has the basically same steps as the example 2, and the only difference is that: the chitosan modified silica gel is replaced by silica gel with equal mass.
Comparative example 3
A method for preparing a phosphogypsum soil conditioner, which has the basically same steps as the example 2, and the only difference is that: the chitosan modified silica gel is replaced by a mixture of chitosan and silica gel with equal mass (common mixing according to a ratio of 1: 1).
And (3) effect detection: selecting acidified soil polluted by heavy metals, dividing the soil into seven areas, diluting the soil conditioner prepared in the above examples 1-3 and comparative examples 1-3 by 100 times with water, and mixing at a ratio of 0.5kg/m2The dosage of the active ingredients is uniformly sprayed in six areas respectively, and the other area is not sprayed as a blank case. The same variety of potatoes are sown in seven areas and are treated conventionally. Observing the growth vigor of potato crops in each area, measuring the average pH value of soil in each area, detecting the content of heavy metal ions (cadmium, chromium, mercury and lead) in potatoes when the potatoes are ripe, and counting the detection results as follows:
as can be seen from the above table, the soil conditioner prepared in the embodiments 1-3 of the present invention all have outstanding effects, which make the pH value of the soil tend to be neutral, make the growth of crops good, and make the heavy metal content in the crops all meet the related limit value regulation in the national standard GB 2762 + 2005 pollutant limit in food.
As can be seen from comparative examples 1 and 2, the effect of adding chitosan and silica gel alone is not ideal, wherein when chitosan is added alone, although the chitosan can adsorb and fix heavy metal ions in a targeted manner, the overall fixing ability is limited, and when silica gel is added alone, the fixing ability is also limited; however, the comparative example 3 shows that the simple mixing of chitosan and silica gel cannot achieve the mutual promotion effect, and the heavy metal reduction effect is also poor, which shows that the invention plays a key role in bonding the chitosan and the silica gel into a whole.
The invention also provides a device for implementing the method, which comprises the following steps:
the crushing module is used for crushing the phosphogypsum;
the impurity removal module is used for removing impurities from the crushed phosphogypsum;
the fermentation module is used for fermenting the biomass fibers doped with the microbial agent;
the mixing module is used for mixing the fermentation product with the phosphogypsum powder, the limestone and the chitosan modified silica gel and stirring the mixture;
and the drying module is used for drying the mixture after stirring treatment.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. A method for preparing a phosphogypsum soil conditioner is characterized by comprising the following steps: comprises the steps of
The method comprises the following steps: firstly crushing the phosphogypsum, and then removing impurities to remove organic matters and soluble impurities in the phosphogypsum to obtain phosphogypsum powder;
step two: selecting biomass fibers doped with a microbial agent, fermenting, mixing a fermentation product with the phosphogypsum powder, and simultaneously adding limestone and chitosan modified silica gel to obtain a mixture;
step three: and stirring the mixture, and drying to obtain the phosphogypsum soil conditioner.
2. A method for preparing a phosphogypsum soil improver according to claim 1, which is characterized in that: the impurity removal treatment is one or the combination of a chemical method, a physical method or a heat treatment method.
3. A method for preparing a phosphogypsum soil improver according to claim 1, which is characterized in that: the microbial agent is one or more of saccharomycetes, bacillus subtilis, bacillus licheniformis, astragalus root nodule bacteria, bacillus laterosporus, bacillus megaterium, trichoderma harzianum or streptomyces microflavus;
the biomass fiber is selected from one or more of straw fiber, bamboo fiber, wood fiber, bagasse fiber, rice hull fiber and wheat bran fiber.
4. A method for preparing a phosphogypsum soil improver according to claim 1, which is characterized in that: the stirring treatment refers to stirring for 2-10h at the rotating speed of 500-1200 r/min.
5. A method for preparing a phosphogypsum soil improver according to claim 1, which is characterized in that: the preparation method of the chitosan modified silica gel comprises the following steps:
(1) selecting silica gel particles with the particle size of 0.1-0.5 mu m, soaking the silica gel particles in 2-6mol/L phosphoric acid for 12-18h, washing the silica gel particles to be neutral by deionized water, and drying the silica gel particles at 80-120 ℃ to constant weight to obtain a silica gel matrix for later use;
(2) mixing N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and 60-80 vt% ethanol solution according to the proportion of 1g:15-20mL, stirring until the N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane is completely dissolved, and standing for 8-20h to obtain a coupling solution for later use;
(3) mixing chitosan and low molecular alcohol according to the proportion of 1g:30-50mL, adding an activating agent accounting for 0.5-2% of the total volume of the system, and performing ultrasonic dispersion for 3-5min to obtain a chitosan modified solution for later use;
(4) and mixing the silica gel matrix, the coupling solution and the chitosan modified solution, heating and refluxing for 4-8h at 75-85 ℃, and washing and drying after solid-liquid separation to obtain the chitosan modified silica gel.
6. A method for preparing a phosphogypsum soil improver according to claim 5, which is characterized in that: the low molecular alcohol is one of methanol, ethanol or isopropanol.
7. A method for preparing a phosphogypsum soil improver according to claim 5, which is characterized in that: the washing and drying refer to: washing with deionized water, washing with acetone solution, and drying at room temperature.
8. A method for preparing a phosphogypsum soil improver according to claim 5, which is characterized in that: the activator is zinc salt or nickel salt.
9. A method for preparing a phosphogypsum soil improver according to claim 1, which is characterized in that: the mass ratio of the fermentation product to the phosphogypsum powder to the limestone to the chitosan modified silica gel is 1:5-10:2-4: 0.5-1.5.
10. An apparatus for carrying out the method of any one of claims 1 to 9, wherein: the device comprises
The crushing module is used for crushing the phosphogypsum;
the impurity removal module is used for removing impurities from the crushed phosphogypsum;
the fermentation module is used for fermenting the biomass fibers doped with the microbial agent;
the mixing module is used for mixing the fermentation product with the phosphogypsum powder, the limestone and the chitosan modified silica gel and stirring the mixture;
and the drying module is used for drying the mixture after stirring treatment.
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| CN115638415A (en) * | 2022-10-20 | 2023-01-24 | 南京师范大学 | Coupling treatment method for enrichment plants, municipal sludge and phosphogypsum |
| CN116000048A (en) * | 2022-12-13 | 2023-04-25 | 天津师范大学 | Phosphogypsum innocent treatment method |
| CN116196908A (en) * | 2022-12-14 | 2023-06-02 | 湖北三峡实验室 | Preparation method and application of a modified phosphogypsum solid-phase microextraction fiber |
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