CN114716269A - Method for preparing citrate soluble fertilizer by roasting, detoxifying and activating asbestos tailings or nickel-iron slag - Google Patents
Method for preparing citrate soluble fertilizer by roasting, detoxifying and activating asbestos tailings or nickel-iron slag Download PDFInfo
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- CN114716269A CN114716269A CN202210329760.1A CN202210329760A CN114716269A CN 114716269 A CN114716269 A CN 114716269A CN 202210329760 A CN202210329760 A CN 202210329760A CN 114716269 A CN114716269 A CN 114716269A
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- nickel
- roasting
- asbestos tailings
- iron slag
- activating
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- 239000010425 asbestos Substances 0.000 title claims abstract description 82
- 229910052895 riebeckite Inorganic materials 0.000 title claims abstract description 82
- 239000002893 slag Substances 0.000 title claims abstract description 56
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003337 fertilizer Substances 0.000 title claims abstract description 43
- 230000003213 activating effect Effects 0.000 title claims abstract description 32
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 21
- 239000011651 chromium Substances 0.000 claims abstract description 21
- 238000007885 magnetic separation Methods 0.000 claims abstract description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012320 chlorinating reagent Substances 0.000 claims abstract description 15
- 230000004913 activation Effects 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims description 36
- 238000000498 ball milling Methods 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 19
- 239000002699 waste material Substances 0.000 abstract description 6
- 239000000835 fiber Substances 0.000 abstract description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 5
- 239000011707 mineral Substances 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000001784 detoxification Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000008521 reorganization Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 15
- 238000001994 activation Methods 0.000 description 11
- 229910000863 Ferronickel Inorganic materials 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000008188 pellet Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000011490 mineral wool Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- BCFSVSISUGYRMF-UHFFFAOYSA-N calcium;dioxido(dioxo)chromium;dihydrate Chemical compound O.O.[Ca+2].[O-][Cr]([O-])(=O)=O BCFSVSISUGYRMF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 235000010585 Ammi visnaga Nutrition 0.000 description 1
- 244000153158 Ammi visnaga Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010023825 Laryngeal cancer Diseases 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000171 calcio olivine Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001691 hercynite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 206010023841 laryngeal neoplasm Diseases 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- -1 silicon-magnesium-calcium-oxygen compounds Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D3/00—Calcareous fertilisers
- C05D3/04—Calcareous fertilisers from blast-furnace slag or other slags containing lime or calcium silicates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for preparing citrate soluble fertilizer by roasting, detoxifying and activating asbestos tailings or nickel-iron slag. The invention firstly carries out magnetic separation on asbestos tailings or nickel-iron slag to remove heavy metals, and then adds an activating agent and a fluxing agent to carry out high-temperature activation roasting to ensure that SiO in the asbestos tailings or the nickel-iron slag2Crystals of minerals such as MgO, CaO and the like realize structural reorganization and become fertilizer components capable of being absorbed by plants; and finally, adding a chlorinating agent to perform chloridizing roasting in a reducing gas atmosphere to further remove heavy metal chromium, thereby solving the problem of incomplete removal of the heavy metal chromium. The invention can realize comprehensive detoxification of the asbestos tailings or the nickel-iron slag, including the removal of heavy metals and asbestos short fibers, and can realize full-element utilization of the asbestos tailings or the nickel-iron slag, thereby really achieving the aims of changing waste into valuable and recycling.
Description
Technical Field
The invention belongs to the technical field of solid waste resource utilization, and particularly relates to a method for preparing citrate soluble fertilizer by roasting, detoxifying and activating asbestos tailings or nickel iron slag.
Background
Asbestos is a natural fibrous mineral that is exploited and used on a large scale as an important fire-proof, insulating and heat-insulating material because of its high fire-resistance, electrical insulation and thermal insulation properties. China is the third largest rock wool reserve country in the world, but the rock wool ore in China contains low rock wool content, and the produced tailings are extremely large. A large amount of asbestos is produced every year, and a large amount of asbestos tailings are produced. However, most asbestos tailings are not effectively treated and can only be stacked, and a large amount of stacked asbestos tailings are a potential geological hazard, occupy land resources and seriously damage the ecological environment. And the asbestos contains a large amount of fine short fibers, and long-term inhalation can cause asbestos lung, lung cancer, laryngeal cancer and the like, thereby being harmful to human health. The ferronickel slag is industrial waste slag generated by water quenching and quenching after reduction and extraction of nickel and partial iron, has huge annual emission, and has the main treatment modes of stacking treatment and deep sea landfill, thereby not only occupying land and polluting environment, but also bringing serious challenge to the sustainable development of ferronickel smelting.
The main chemical components of the asbestos tailings and the nickel-iron slag are SiO2And MgO, which has important value in utilization, so that the asbestos tailings and the accumulated nickel-iron slag can cause a great deal of waste of important resources. At present, the valuable component extraction of asbestos tailings and nickel-iron slag and other non-metallic materials have complex preparation process and high economic cost, most of the valuable components can be extracted only by single component, the all elements cannot be utilized, and the obtained products have undersized market, low added value and poor economic benefit.
Researches show that the asbestos tailings and the nickel-iron slag contain rich elements such as magnesium, silicon, calcium and iron, so that the asbestos tailings and the nickel-iron slag have a great prospect when applied to agricultural fertilizers, but the existing researches and technologies are not generally developed and mature, and the asbestos tailings are crushed (patent publication No. CN109020629) and put into a ball mill for ball milling and added with KCl for producing chemical fertilizer powder, so that the defects that heavy metals in the asbestos tailings are not effectively and comprehensively removed, the asbestos tailings cannot be directly applied to agricultural production, and further resource utilization is influenced are overcome; the ore smelting furnace is used for melting asbestos tailings and graphite, and screening and recovering iron, cobalt, nickel and chromium to serve as a medium trace element fertilizer, but the process does not consider the problem of activation of silicon and magnesium elements, the melting temperature of the ore smelting furnace can reach about 1500 ℃, the energy consumption is too high, the production cost is too high, and large-scale batch production cannot be carried out. In terms of resource utilization of ferronickel slag, the research on the field of construction is the most, and the recovery of useful metal elements is still in the early stage.
In conclusion, a process technology which can completely remove heavy metals, recycle asbestos tailings and nickel-iron slag and fully activate silicon and magnesium elements in the asbestos tailings and the nickel-iron slag to be used as citrate soluble fertilizer does not exist at present. The application of the asbestos tailings and the nickel-iron slag in the aspect of agricultural fertilizers can not only effectively realize the full resource utilization of the tailings and the waste slag, but also obtain products with higher added value, and have larger application and market prospects although a great deal of research progress is not carried out at present.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a method for preparing a citrate soluble fertilizer by roasting, detoxifying/activating asbestos tailings or nickel-iron slag.
The purpose of the invention is realized by the following technical scheme:
a method for preparing citrate soluble fertilizer by roasting, detoxifying/activating asbestos tailings or nickel-iron slag comprises the following steps:
(1) crushing asbestos tailings or nickel-iron slag, ball-milling, and magnetically separating iron, nickel, chromium and cobalt to obtain an iron alloy fine powder product;
(2) grinding and uniformly mixing the asbestos tailings or the nickel-iron slag subjected to magnetic separation in the step (1) with an activating agent and a fluxing agent, adding water for granulation, heating to 800-1000 ℃, and performing high-temperature roasting activation reaction to obtain an active roasting product;
(3) and (3) cooling the active roasting product obtained in the step (2), then carrying out ball milling, then grinding and uniformly mixing with a chlorinating agent, heating in a reducing gas atmosphere for carrying out chlorination roasting, cooling, and then carrying out ball milling to obtain the citrate soluble fertilizer powder.
Preferably, the crushing in step (1) is performed by using a jaw crusher.
Preferably, the ball milling in the step (1) is ball milling to 100-200 meshes.
Preferably, the activating agent in step (2) is at least one of calcium carbonate, calcium oxide and calcium hydroxide; the mass ratio of the asbestos tailings or the nickel-iron slag subjected to magnetic separation to the activating agent is 1: 0.3 to 0.5.
Preferably, the fluxing agent in the step (2) is at least one of potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate; the mass ratio of the asbestos tailings or the nickel-iron slag subjected to magnetic separation to the fluxing agent is 1: 0.02-0.05.
Preferably, the water adding granulation in the step (2) is to add water into the uniformly mixed raw material to prepare small material balls with the diameter of 8-10 mm, so that sintering is facilitated, and in order to prevent the ball bursting phenomenon during high-temperature roasting, each small ball is perforated by a toothpick so as to discharge carbon dioxide and water.
Preferably, the heating rate of the heating in the step (2) is 5-10 ℃/min; and after the temperature is raised to 800-1000 ℃, the temperature is kept for 120-150 min.
Preferably, the ball milling in the step (3) refers to ball milling to 100-200 meshes.
Preferably, the chlorinating agent in the step (3) is at least one of calcium chloride, potassium chloride, sodium chloride, magnesium chloride, ferric chloride and ammonium chloride; the mass ratio of the asbestos tailings or the nickel-iron slag subjected to magnetic separation to the chlorinating agent is 1: 0.15 to 0.2.
Preferably, the reducing gas in step (3) is one of hydrogen or ammonia.
Preferably, the heating rate of the heating in the step (3) is 5 ℃/min; the temperature rise is 350-550 ℃, and the heat preservation time is 60-90 min.
The principle of the invention is as follows:
(1) firstly, aiming at the magnetic characteristics of metal elements (Fe, Ni, Cr and Co) contained in asbestos tailings or nickel-iron slag, the asbestos tailings or the nickel-iron slag are magnetically separated, heavy metals can be effectively removed after the magnetic separation, and the heavy metals and the iron elements are enriched to form a byproduct iron alloy fine powder.
(2) And adding an activating agent and a fluxing agent into the tailings or the waste residues after impurity removal to perform high-temperature activated roasting. Firstly, the added fluxing agent is strong alkali, so that the melting point can be obviously reduced, and the reaction temperature is reduced to 800-1000 ℃, thereby greatly reducing the energy consumption. Secondly, the added activating agent and silicon are subjected to solid-phase reaction to generate soluble Ca2SiO4And leading SiO in asbestos tailings or nickel-iron slag2And the crystals of minerals such as MgO, CaO and the like realize structural reorganization and become fertilizer components capable of being absorbed by plants. Meanwhile, the activity of the mineral substances can be effectively increased through high-temperature roasting, so that the trace elements in the mineral substances in the product can be absorbed by plants more easily. And thirdly, chromium in the tailings or waste residues is trivalent chromium which exists in the form of hercynite and is difficult to remove, and the hexavalent chromium which is easy to react is generated after high-temperature activation roasting and exists in the form of calcium chromate. The activation process is as follows:
(3) and adding a chlorinating agent into the activated product after high-temperature roasting for chloridizing roasting at the temperature of 350-550 ℃ in a reducing gas atmosphere, reacting calcium chromate with the chlorinating agent to generate low-boiling chromium trichloride hexahydrate, and completely volatilizing in the roasting process, so that the problem that the heavy metal chromium is not completely removed is solved. The reduction chlorination process is as follows:
compared with the prior art, the invention has the following advantages and beneficial effects:
firstly, obtaining an iron alloy fine powder product with a high added value through magnetic separation, so that most heavy metals are removed; then, an activator and a fluxing agent are added for activated roasting, so that the silicon, magnesium and calcium elements are changed into soluble and released to prepare a fertilizer with a high added value, the reaction temperature is obviously reduced, the reaction efficiency is improved, and compared with a submerged arc furnace melting reaction, the production energy consumption is greatly reduced; and then chlorination roasting is carried out by adding a chlorinating agent, so that heavy metal chromium is further removed. The invention can realize comprehensive detoxification of the asbestos tailings or the nickel-iron slag, including the removal of heavy metals and asbestos short fibers, and can realize full-element utilization of the asbestos tailings or the nickel-iron slag, thereby really achieving the aims of changing waste into valuable and recycling.
Drawings
FIG. 1 is a process flow diagram of the method of the present invention.
FIG. 2 is a physical diagram of the pellets of example 1, wherein (a) is raw pellets before high-temperature activation and calcination of asbestos tailings, and (b) is cooked pellets after high-temperature activation and calcination of asbestos tailings.
FIG. 3 is XRD patterns of asbestos tailings (a) subjected to magnetic separation in the example of the invention and citric acid-soluble fertilizer powder (b) obtained in the example 1.
FIG. 4 is an electron microscope image of asbestos tailings as such (a) and citric acid-soluble fertilizer powder (b) obtained in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
The specific compositions of the asbestos tailings and the nickel iron ore used in the following examples and comparative examples are shown in tables 1 and 2:
TABLE 1 asbestos tailings main Components
TABLE 2 main components of nickel iron ore
Example 1
(1) Crushing asbestos tailings by using a jaw crusher, then adding the crushed asbestos tailings into a ball mill to be ball-milled to about 200 meshes, and selecting iron, nickel, chromium and cobalt from the ball-milled asbestos tailings powder by using a belt conveyor magnetic separation system to obtain an iron alloy fine powder product;
(2) grinding and uniformly mixing 1g of the asbestos tailing powder subjected to magnetic separation, 0.5g of calcium carbonate (activating agent) and 0.02g of potassium hydroxide (fluxing agent), adding water for granulation to prepare small material balls with the diameter of 8-10 mm, then placing the small material balls in a muffle furnace, raising the temperature to 1000 ℃ at the rate of 5 ℃/min, and keeping the temperature for 120min for high-temperature roasting activation reaction;
(3) cooling to room temperature, taking out the mixture from a muffle furnace, ball-milling the mixture to about 200 meshes, grinding and mixing the mixture with 0.2g of potassium chloride (chlorinating agent), placing the mixture in the muffle furnace, raising the temperature to 350 ℃ at a heating rate of 5 ℃/min in a hydrogen atmosphere, and keeping the temperature for 60min to perform chloridizing roasting to remove heavy metal chromium;
(4) cooling to room temperature, taking out from a muffle furnace, and performing ball milling to about 200 meshes to obtain the citrate soluble fertilizer powder.
Example 2
(1) Crushing the ferronickel slag by using a jaw crusher, adding the crushed ferronickel slag into a ball mill, ball-milling the crushed ferronickel slag to about 200 meshes, and selecting iron, nickel, chromium and cobalt from the ball-milled ferronickel slag powder by using a belt conveyor magnetic separation system to obtain an iron alloy fine powder product;
(2) grinding and uniformly mixing 10g of magnetically-separated nickel-iron slag, 4g of calcium hydroxide (activating agent) and 0.5g of sodium hydroxide (fluxing agent), adding water for granulation to prepare small material balls with the diameter of 8-10 mm, then placing the small material balls in a muffle furnace, raising the temperature to 850 ℃ at the rate of 5 ℃/min, and keeping the temperature for 120min for high-temperature roasting activation reaction;
(3) cooling to room temperature, taking out the mixture from a muffle furnace, ball-milling the mixture to about 200 meshes, grinding and mixing the mixture with 1.5g of ammonium chloride (chlorinating agent) uniformly, placing the mixture in the muffle furnace, raising the temperature to 500 ℃ at a heating rate of 5 ℃/min in a hydrogen atmosphere, and keeping the temperature for 60min to perform chloridizing roasting to remove heavy metal chromium;
(4) cooling to room temperature, taking out from a muffle furnace, and performing ball milling to about 200 meshes to obtain the citrate soluble fertilizer powder.
Example 3
(1) Crushing asbestos tailings by using a jaw crusher, then adding the crushed asbestos tailings into a ball mill to be ball-milled to about 200 meshes, and selecting iron, nickel, chromium and cobalt from the ball-milled asbestos tailings powder by using a belt conveyor magnetic separation system to obtain an iron alloy fine powder product;
(2) grinding and uniformly mixing 100g of magnetically-separated asbestos tailing powder, 30g of calcium oxide (an activating agent) and 5g of potassium carbonate (a fluxing agent), adding water for granulation to prepare small material balls with the diameter of 8-10 mm, placing the small material balls in a muffle furnace, raising the temperature to 900 ℃ at the rate of 5 ℃/min, and keeping the temperature for 120min for high-temperature roasting and activating reaction;
(3) cooling to room temperature, taking out the mixture from a muffle furnace, ball-milling the mixture to about 200 meshes, grinding and uniformly mixing the mixture with 15g of calcium chloride (chlorinating agent), placing the mixture in the muffle furnace, raising the temperature to 400 ℃ at a heating rate of 5 ℃/min under a hydrogen atmosphere, and keeping the temperature for 60min for chloridizing roasting to remove heavy metal chromium;
(4) cooling to room temperature, taking out from a muffle furnace, and performing ball milling to about 200 meshes to obtain the citrate soluble fertilizer powder.
Comparative example 1 (600 ℃ C. for the activation baking temperature compared with example 1)
(1) Crushing asbestos tailings by using a jaw crusher, then adding the crushed asbestos tailings into a ball mill to be ball-milled to about 200 meshes, and selecting iron, nickel, chromium and cobalt from the ball-milled asbestos tailings powder by using a belt conveyor magnetic separation system to obtain an iron alloy fine powder product;
(2) grinding and uniformly mixing 1g of the asbestos tailing powder subjected to magnetic separation, 0.5g of calcium carbonate (activating agent) and 0.02g of potassium hydroxide (fluxing agent), adding water for granulation to prepare small pellets of 8-10 mm, then placing the small pellets into a muffle furnace, raising the temperature to 600 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 120min for high-temperature roasting activation reaction;
(3) cooling to room temperature, taking out the mixture from a muffle furnace, ball-milling the mixture to about 200 meshes, grinding and mixing the mixture with 0.2g of potassium chloride (chlorinating agent) uniformly, placing the mixture in the muffle furnace, raising the temperature to 350 ℃ at a heating rate of 5 ℃/min in a hydrogen atmosphere, and keeping the temperature for 60min to perform chloridizing roasting to remove heavy metal chromium;
(4) cooling to room temperature, taking out from a muffle furnace, and performing ball milling to about 200 meshes to obtain the citrate soluble fertilizer powder.
Comparative example 2 (2 g of calcium hydroxide as compared with example 2, with the amount of the activator used being changed)
(1) Crushing the ferronickel slag by using a jaw crusher, adding the crushed ferronickel slag into a ball mill, performing ball milling to about 200 meshes, and selecting iron, nickel, chromium and cobalt from the nickel-iron slag powder subjected to ball milling by using a belt conveyor magnetic separation system to obtain an iron alloy fine powder product;
(2) grinding and uniformly mixing 10g of magnetically-separated nickel-iron slag, 2g of calcium hydroxide (activating agent) and 0.5g of sodium hydroxide (fluxing agent), adding water for granulation, preparing into small pellets of 8-10 mm, placing the small pellets into a muffle furnace, raising the temperature to 850 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 120min for high-temperature roasting and activating reaction;
(3) cooling to room temperature, taking out the mixture from a muffle furnace, ball-milling the mixture to about 200 meshes, grinding and mixing the mixture with 1.5g of ammonium chloride (chlorinating agent) uniformly, placing the mixture in the muffle furnace, raising the temperature to 500 ℃ at a heating rate of 5 ℃/min in a hydrogen atmosphere, and keeping the temperature for 60min to perform chloridizing roasting to remove heavy metal chromium;
(4) cooling to room temperature, taking out from a muffle furnace, and performing ball milling to about 200 meshes to obtain the citrate soluble fertilizer powder.
Example 4
0.3g of citric acid-soluble fertilizer powder obtained in examples 1 to 3 and comparative examples 1 to 2 was weighed out and added to 30mL of 2% citric acid solution, and mixed and dissolved at 25 ℃ and 250rpm on a constant temperature shaking table for 120 min. The dissolution rates of silicon and magnesium in citric acid in the citrate-soluble fertilizer powders obtained in examples 1 to 3 and comparative examples 1 to 2 were quantitatively analyzed by ICP as shown in Table 3.
TABLE 3 elution rates of silicon and magnesium in citric acid in citrate soluble fertilizer powders
Example 5
And (3) detecting the product prepared by the implementation:
as shown in fig. 3, XRD patterns of the asbestos tailings after magnetic separation and the citrate-soluble fertilizer powder obtained in example 1 show that the asbestos tailings after magnetic separation (a in fig. 3) are complex phases of a plurality of silicon-magnesium-calcium-oxygen compounds, silicon and magnesium are not released and cannot be used as fertilizer, and XRD patterns of the citrate-soluble fertilizer powder obtained after high-temperature activation (b in fig. 3) show that the phases of the complex compounds disappear and calcium silicate and magnesium oxide appear, indicating that citrate-soluble silicon and magnesium are released in large quantities.
As shown in fig. 4, the electron microscope images of the asbestos tailings and the citric acid-soluble fertilizer powder obtained in example 1 are shown. From the electron microscope image (a in fig. 4) of the asbestos tailings as it is, it is known that the asbestos tailings contain a large amount of fine short fibers, while the electron microscope image (b in fig. 4) of the citrate soluble fertilizer powder obtained in example 1 shows that the asbestos short fibers disappear, and the asbestos tailings are completely detoxified after high-temperature roasting.
The results of the quantitative analysis of the XRF components of the citrate soluble fertilizer powders obtained in the examples 1-3 are shown in the table 4, and it can be seen that the mass fractions of the heavy metal chromium in the examples 1-3 are all less than 0.05% specified in the national standard (GB/T36207-2018), and further the successful removal of the heavy metal in the asbestos tailings treated by the method is proved.
TABLE 4 analysis of XRF chemical composition of citrate soluble fertilizer powders
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for preparing citrate soluble fertilizer by roasting, detoxifying and activating asbestos tailings or nickel-iron slag is characterized by comprising the following steps:
(1) crushing asbestos tailings or nickel-iron slag, ball-milling, and magnetically separating iron, nickel, chromium and cobalt to obtain an iron alloy fine powder product;
(2) grinding and uniformly mixing the asbestos tailings or the nickel-iron slag subjected to magnetic separation in the step (1) with an activating agent and a fluxing agent, adding water for granulation, heating to 800-1000 ℃, and performing high-temperature roasting activation reaction to obtain an active roasting product;
(3) and (3) cooling the active roasting product obtained in the step (2), then carrying out ball milling, then grinding and uniformly mixing with a chlorinating agent, heating in a reducing gas atmosphere for carrying out chlorination roasting, cooling, and then carrying out ball milling to obtain the citrate soluble fertilizer powder.
2. The method for preparing citrate soluble fertilizer by roasting, detoxifying and activating asbestos tailings or nickel iron slag according to claim 1, wherein the activating agent in the step (2) is at least one of calcium carbonate, calcium oxide and calcium hydroxide; the mass ratio of the asbestos tailings or the nickel-iron slag subjected to magnetic separation to the activating agent is 1: 0.3 to 0.5.
3. The method for preparing citrate soluble fertilizer by roasting, detoxifying and activating asbestos tailings or nickel-iron slag according to claim 1, wherein the temperature in the step (2) is increased to 800-1000 ℃ and then is kept for 120-150 min.
4. The method for preparing citrate soluble fertilizer by roasting, detoxifying and activating asbestos tailings or nickel-iron slag according to claim 1, wherein the fluxing agent in the step (2) is at least one of potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate; the mass ratio of the asbestos tailings or the nickel-iron slag subjected to magnetic separation to the fluxing agent is 1: 0.02-0.05.
5. The method for preparing citrate soluble fertilizer by roasting, detoxifying and activating asbestos tailings or nickel iron slag according to claim 1, wherein the chlorinating agent in the step (3) is at least one of calcium chloride, potassium chloride, sodium chloride, magnesium chloride, ferric chloride and ammonium chloride; the mass ratio of the asbestos tailings or the nickel-iron slag subjected to magnetic separation to the chlorinating agent is 1: 0.15 to 0.2.
6. The method for preparing citrate soluble fertilizer by roasting, detoxifying and activating asbestos tailings or nickel-iron slag according to claim 1, wherein the temperature rise in the step (3) is 350-550 ℃, and the heat preservation time is 60-90 min.
7. The method for preparing citrate soluble fertilizer by roasting, detoxifying and activating asbestos tailings or nickel-iron slag according to claim 1, wherein the reducing gas in the step (3) is one of hydrogen gas or ammonia gas.
8. The method for preparing citrate soluble fertilizer by roasting, detoxifying and activating asbestos tailings or nickel-iron slag according to claim 1, wherein the ball milling in the steps (1) and (3) is performed to 100-200 meshes.
9. The method for preparing citrate soluble fertilizer by roasting, detoxifying and activating asbestos tailings or nickel-iron slag according to claim 1, wherein the step (2) of adding water for granulation is to add water into the uniformly mixed raw materials to prepare small material balls with the diameter of 8-10 mm.
10. The method for preparing citrate soluble fertilizer by roasting, detoxifying and activating asbestos tailings or nickel-iron slag according to claim 1, wherein the temperature rise rate of the temperature rise in the steps (2) and (3) is 5-10 ℃/min.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106365915A (en) * | 2016-09-10 | 2017-02-01 | 上海大学 | Method for preparing silicon-magnesium-phosphorus-potassium composite fertilizer from serpentine |
| CN106396746A (en) * | 2016-09-10 | 2017-02-15 | 上海大学 | Method for preparing silicon-magnesium-potassium-sulfur compound fertilizer from serpentine prepared by activation alkali fusion method |
| CN108484243A (en) * | 2018-05-21 | 2018-09-04 | 广东中金岭南环保工程有限公司 | A kind of multiple-effect solubility in citric acid siliceous fertilizer and its preparation method and application |
| CN109020629A (en) * | 2018-09-05 | 2018-12-18 | 若羌县圣地石棉尾料再利用科技开发有限公司 | A kind of technique using asbestos tailings production Si, Ca, Mg, K fertilizer |
| CN109266841A (en) * | 2018-11-27 | 2019-01-25 | 广东工业大学 | A kind of calcination process method of iron tailings |
| CN111410576A (en) * | 2020-03-16 | 2020-07-14 | 华南理工大学 | Method for realizing asbestos tailing detoxification and recycling by using activation and co-reduction method |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106365915A (en) * | 2016-09-10 | 2017-02-01 | 上海大学 | Method for preparing silicon-magnesium-phosphorus-potassium composite fertilizer from serpentine |
| CN106396746A (en) * | 2016-09-10 | 2017-02-15 | 上海大学 | Method for preparing silicon-magnesium-potassium-sulfur compound fertilizer from serpentine prepared by activation alkali fusion method |
| CN108484243A (en) * | 2018-05-21 | 2018-09-04 | 广东中金岭南环保工程有限公司 | A kind of multiple-effect solubility in citric acid siliceous fertilizer and its preparation method and application |
| CN109020629A (en) * | 2018-09-05 | 2018-12-18 | 若羌县圣地石棉尾料再利用科技开发有限公司 | A kind of technique using asbestos tailings production Si, Ca, Mg, K fertilizer |
| CN109266841A (en) * | 2018-11-27 | 2019-01-25 | 广东工业大学 | A kind of calcination process method of iron tailings |
| CN111410576A (en) * | 2020-03-16 | 2020-07-14 | 华南理工大学 | Method for realizing asbestos tailing detoxification and recycling by using activation and co-reduction method |
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