CN113086958A - Preparation method of blast furnace slag-based composite material - Google Patents
Preparation method of blast furnace slag-based composite material Download PDFInfo
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- CN113086958A CN113086958A CN202110366273.8A CN202110366273A CN113086958A CN 113086958 A CN113086958 A CN 113086958A CN 202110366273 A CN202110366273 A CN 202110366273A CN 113086958 A CN113086958 A CN 113086958A
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- furnace slag
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- 239000002893 slag Substances 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000000047 product Substances 0.000 claims description 29
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 229910000805 Pig iron Inorganic materials 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 238000009628 steelmaking Methods 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims 1
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims 1
- 229910000389 calcium phosphate Inorganic materials 0.000 claims 1
- 235000019700 dicalcium phosphate Nutrition 0.000 claims 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims 1
- 235000019691 monocalcium phosphate Nutrition 0.000 claims 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims 1
- 235000019796 monopotassium phosphate Nutrition 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims 1
- 239000011736 potassium bicarbonate Substances 0.000 claims 1
- 235000015497 potassium bicarbonate Nutrition 0.000 claims 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims 1
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 235000011181 potassium carbonates Nutrition 0.000 claims 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims 1
- 235000011118 potassium hydroxide Nutrition 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 239000001488 sodium phosphate Substances 0.000 claims 1
- 229910000162 sodium phosphate Inorganic materials 0.000 claims 1
- 229960003339 sodium phosphate Drugs 0.000 claims 1
- 235000011008 sodium phosphates Nutrition 0.000 claims 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 28
- 239000010457 zeolite Substances 0.000 abstract description 28
- 230000008569 process Effects 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000004927 fusion Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000002440 industrial waste Substances 0.000 abstract description 2
- 230000032683 aging Effects 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000001994 activation Methods 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 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
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
-
- 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
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
Abstract
The invention discloses a preparation method of a blast furnace slag-based composite material, and belongs to the technical field of industrial waste residue recycling. The invention mainly comprises the following steps: (1) the blast furnace slag is subjected to alkali fusion, (2) the blast furnace slag reacts with phosphate, and (3) the blast furnace slag-based hydroxyapatite-zeolite composite material with high added value is prepared through hydrothermal aging, so that the comprehensive utilization of useful components in the blast furnace slag is realized. The method has the characteristics of strong adaptability, simple process, convenient operation, mild reaction condition, high product added value and the like; the method of the invention takes the blast furnace slag as a cheap raw material, which not only can effectively relieve the environmental problem caused by the large amount of stockpiling of the blast furnace slag, but also can reduce the construction and operation cost of an enterprise yard to a certain extent.
Description
Technical Field
The invention belongs to the technical field of industrial waste residue recycling, mainly relates to a preparation method of a blast furnace slag-based composite material, and particularly relates to a preparation method of a blast furnace slag-based hydroxyapatite-zeolite composite material.
Background
Blast furnace slag, which is a major by-product of high-furnace iron making, is mainly composed of gangue in iron ore, ash in coke, flux and other impurities that cannot enter pig iron. Along with the development of the iron and steel industry in China, the discharge amount of blast furnace slag is increased day by day, a large amount of blast furnace slag is discharged and stacked, if reasonable resource utilization is carried out on the blast furnace slag without increasing the strength, a large amount of resource waste is caused, and the problem of land resource occupation, environmental pollution and the like is caused by a large amount of stacked blast furnace slag. Therefore, the discharge of blast furnace slag has become a difficult problem for steel manufacturing enterprises and society, and how to safely dispose and efficiently utilize the blast furnace slag hill becomes a major problem to be solved.
At present, the comprehensive utilization rate of the blast furnace slag in China is still lower than that of developed countries in the world, in recent years, for the problem of blast furnace slag resource, a plurality of scholars have conducted beneficial exploration, and the following utilization ways are developed and designed:
patent CN106185975A discloses a method for preparing molecular sieve crystals by using blast furnace slag, which mainly comprises the following steps: (1) the preparation method comprises the steps of (1) pretreatment of blast furnace slag, (2) reaction with hydrochloric acid, (3) reaction with sodium hydroxide, and (4) preparation of a molecular sieve crystal with a porous structure by a hydrothermal method. Finally, the silica gel with the purity of more than 92 percent, the meta-aluminate with the purity of more than 95 percent and the molecular sieve crystal with the purity of more than 90 percent with high added value are obtained. The recorded technical proposal mainly utilizes the blast furnace slag component in the preparation process as SiO2，Al2O3The utilization of CaO is not involved, and in addition, the process steps are excessive, wherein hydrochloric acid is consumed in a large amount and meaninglessly; meanwhile, the preparation of the molecular sieve product is carried out in a high-pressure autoclave at a high temperature (120-.
The patent CN101397154B discloses a method for preparing a water treatment agent by using blast furnace slag, which is obtained by treating the blast furnace slag with an alkaline solution, wherein the blast furnace slag and the alkaline solution with the pH value of more than 11 are mixed according to the solid-to-liquid ratio of 1:1-5, are filtered, are dried for 24-48 h at the temperature of 50-120 ℃, are taken out, are crushed and finally pass through a standard sieve with 100 meshes, and the improved blast furnace slag-based water treatment agent is prepared. According to the technical scheme, when the blast furnace slag-based water treatment agent is prepared, the blast furnace slag is subjected to alkali fusion treatment by using an alkaline aqueous solution, and because some stable crystalline phases in mineral raw materials, such as crystals of quartz, mullite and the like, are difficult to completely dissolve in an alkaline solution, the gel crystallization process is performed on the surfaces of mineral particles which are not completely dissolved, the problems of low product crystallinity and non-uniform crystalline phases are inevitable, and the utilization rate of blast furnace slag resources is low.
Therefore, the blast furnace slag treatment scheme described in the above patent publication is limited by the product yield, the added value, the process technical conditions and the cost, the progress in the aspect of industrial utilization is slow, and the problems of low blast furnace slag utilization efficiency, complex process, high cost, poor economic benefit, high environmental risk and the like exist in the actual industrial production, so that the requirement for blast furnace slag resource utilization is difficult to meet, and the improvement of the comprehensive utilization level of resources is severely restricted.
Disclosure of Invention
The invention aims to provide a preparation method of a blast furnace slag-based composite material, which makes full use of active ingredients in blast furnace slag to prepare and form the blast furnace slag-based hydroxyapatite-zeolite composite material.
The invention provides a preparation method of a blast furnace slag-based composite material, which comprises the following steps:
the method comprises the following steps: melting blast furnace slag and alkaline medium particles at high temperature to obtain a molten product;
step two: after the molten product reacts with a phosphate solution, adding a NaOH solution, fully mixing and crystallizing to obtain a crystallized product;
step three: and taking out the crystallized product, filtering, washing a filter cake to be neutral, and drying to obtain the blast furnace slag-based composite material.
The invention relates to a preparation method of a blast furnace slag-based composite material, which comprises the following steps of in the first step, in order to fully utilize useful components in blast furnace slag, carrying out alkali-fusion treatment on the blast furnace slag by adopting alkaline medium particles, converting silicon and aluminum which are difficult to treat in the blast furnace slag into soluble silicate and meta-aluminate so as to improve the reaction activity and reduce the reaction time, and carrying out alkali-fusion treatment on the blast furnace slag after the alkaline medium particles are fused at high temperature. In addition, compared with the traditional alkaline aqueous solution synthesis method, the alkali fusion-hydrothermal synthesis process adopting solid alkali as an activating agent can improve the conversion rate of the product and realize the high-efficiency preparation of the product.
According to the preparation method of the blast furnace slag-based composite material, in the second step, the phosphate is adopted for reaction to prepare the hydroxyapatite-zeolite composite material, compared with the traditional phosphoric acid activation method, excessive phosphoric acid is not needed for neutralization, the subsequent use amount of sodium hydroxide can be obviously reduced, and the reaction system is in an alkaline environment, so that good reaction conditions are provided for the preparation of the hydroxyapatite-zeolite composite material.
According to the preparation method of the blast furnace slag-based composite material, the blast furnace slag is preferably steelmaking pig iron slag, and based on the composition of the blast furnace slag and alkali fusion activation treatment, the hydroxyapatite-zeolite composite material can realize a one-pot method, so that the production efficiency can be improved compared with the traditional step-by-step preparation.
In the second step of the preparation method of the blast furnace slag-based composite material, the reaction process of adding the NaOH solution and fully mixing needs violent stirring so as to improve the dispersibility of the product.
After the technical scheme is adopted, the invention mainly has the following effects:
(1) the invention makes full use of the self-composition characteristics of the blast furnace slag and can realize the effect of the blast furnace slagSiO2，CaO，Al2O3The high-efficiency utilization of the main components; the method can be carried out at the normal pressure and the temperature of 80-100 ℃, and has obvious safety advantage compared with the method carried out at the higher temperature (120-;
(2) compared with the traditional method for preparing the product after the strong acid activation treatment, the method does not relate to the strong acid activation treatment, on one hand, the addition amount of alkali in the subsequent treatment process is reduced, on the other hand, the potential leakage of heavy metal in the blast furnace slag in the strong acid activation process is not caused, and the method has good environmental friendliness;
(3) compared with the traditional method for preparing the product after the strong acid activation treatment, the method has the advantages that the refractory alumino-silicate in the blast furnace slag is converted into soluble silicate and meta-aluminate to improve the reaction activity and remarkably reduce the preparation time, the reaction time is required to be more than 3 days in the traditional strong acid activation-alkali dissolution hydrothermal reaction, and the corresponding product can be prepared after the reaction is carried out for 6-10 hours;
(4) the method provided by the invention is used for treating the blast furnace slag, the reaction is carried out for 6-10 hours at 80-100 ℃, and the hydroxyapatite-zeolite composite material can be prepared, 86.56g of the hydroxyapatite-zeolite composite material can be prepared per 100g of the blast furnace slag, and the method has the characteristics of high decrement efficiency, high recovery rate of useful components, simple process, mild conditions and the like;
(5) the blast furnace slag-based hydroxyapatite-zeolite composite material prepared by the invention can be widely applied to the water treatment process and respectively treats 50mg/L of Mn at room temperature2+，NH4 +，HPO4 2-The adsorption capacity of the composite material is 24.68-26.58 mg/g, 20.10-23.08 mg/g and 24.40-26.41 mg/g, the adsorption level of the composite material on phosphate can completely reach the adsorption capacity of the product prepared by the traditional strong acid activation-alkali dissolution hydrothermal reaction on phosphate, and the blast furnace slag-based hydroxyapatite-zeolite composite material prepared by the invention canAt the same timeThe ammonium salt, the heavy metal and the phosphate are adsorbed, and the good adsorption effect is achieved;
(6) the invention has the characteristics of cheap raw materials, simple required equipment and the like, further reduces the production cost, is beneficial to popularization and utilization, and thus forms a new environment-friendly and efficient recycling process of blast furnace slag resources.
Drawings
FIG. 1 is an SEM image of a blast furnace slag-based hydroxyapatite-zeolite composite material prepared in example 1;
FIG. 2 is an XRD pattern of a blast furnace slag-based hydroxyapatite-zeolite composite material prepared in example 1;
FIG. 3 is an elemental analysis spectrum of a blast furnace slag-based hydroxyapatite-zeolite composite material prepared in example 1;
FIG. 4 is an SEM image of a blast furnace slag-based hydroxyapatite-zeolite composite material prepared in example 2;
FIG. 5 is an XRD pattern of a blast furnace slag-based hydroxyapatite-zeolite composite material prepared in example 2;
FIG. 6 is an elemental analysis spectrum of a blast furnace slag-based hydroxyapatite-zeolite composite material prepared in example 2;
FIG. 7 is an SEM image of a blast furnace slag-based hydroxyapatite-zeolite composite material prepared in example 3;
FIG. 8 is an XRD pattern of a blast furnace slag-based hydroxyapatite-zeolite composite material prepared in example 3;
fig. 9 is an elemental analysis map of the blast furnace slag-based hydroxyapatite-zeolite composite material prepared in example 3.
Detailed Description
The invention is further illustrated, but is not limited, by the following examples in which all percentages are by mass unless otherwise specified.
Example 1
The blast furnace slag is collected from a certain steel member company Limited in Jiangsu, and comprises the following main components: SiO 2229.13％，CaO 47.08％，Al2O320.59 percent and 1.11 percent of MgO. The preparation method of the blast furnace slag-based hydroxyapatite-zeolite composite material comprises the following steps:
(1) uniformly mixing blast furnace slag and sodium hydroxide according to the mass ratio of 1:1.3, and melting at 600 ℃ for 60min to obtain a molten product;
(2) controlling the Ca/P molar ratio of a reaction system to be 10:6, transferring the molten product obtained in the step (1) into a three-neck flask, adding 30mL of 2.0mol/L disodium hydrogen phosphate solution, stirring uniformly, continuing adding 50mL of 2.0mol/L NaOH solution, stirring vigorously at 100 ℃ for 1h, and crystallizing for 6 h;
(3) and (3) after the crystallization in the step (2) is finished, taking out the product, filtering, washing a filter cake to be neutral, drying for 3 hours at 80 ℃ to obtain the blast furnace slag-based hydroxyapatite-zeolite composite material, wherein the microstructure, phase composition and element analysis of the prepared blast furnace slag-based hydroxyapatite-zeolite composite material are respectively shown in a figure 1, a figure 2 and a figure 3. The adsorption capacity test is carried out on the Mn-Mn composite material, and the results show that the Mn-Mn composite material respectively treats 50mg/L of Mn at room temperature2+，NH4 +，HPO4 2-The adsorption treatment is carried out, and the adsorption capacities are respectively as high as 25.98mg/g, 20.10mg/g and 26.41 mg/g.
Example 2
The blast furnace slag is the same as the example 1, and the preparation steps of the blast furnace slag-based hydroxyapatite-zeolite composite material are as follows:
(1) uniformly mixing blast furnace slag and sodium hydroxide particles according to the mass ratio of 1:1.3, and melting at 550 ℃ for 60min to obtain a molten product;
(2) controlling the Ca/P molar ratio of a reaction system to be 10:6, transferring the molten product obtained in the step (1) into a three-neck flask, adding 30mL of 2.0mol/L sodium dihydrogen phosphate solution, stirring uniformly, continuing adding 50mL of 2.0mol/L NaOH solution, stirring vigorously at 100 ℃ for 2h, and crystallizing for 8 h;
(3) and (3) after the crystallization in the step (2) is finished, taking out the product, filtering, washing a filter cake to be neutral, and drying for 3 hours at 80 ℃ to obtain the blast furnace slag-based hydroxyapatite-zeolite composite material. The microstructure, phase composition and elemental analysis of the prepared blast furnace slag-based hydroxyapatite-zeolite composite material are respectively shown in fig. 4, fig. 5 and fig. 6. The adsorption capacity test is carried out on the Mn-Mn composite material, and the results show that the Mn-Mn composite material respectively treats 50mg/L of Mn at room temperature2+，NH4 +，HPO4 2-The adsorption capacity of the adsorbent is up to 24.68mg/g and 22.10 mg/g respectivelymg/g and 24.40 mg/g.
Example 3
The blast furnace slag is the same as the example 1, and the preparation steps of the blast furnace slag-based hydroxyapatite-zeolite composite material are as follows:
(1) uniformly mixing blast furnace slag and sodium hydroxide particles according to the mass ratio of 1:1.2, and melting at 500 ℃ for 120min to obtain a molten product;
(2) controlling the Ca/P molar ratio of a reaction system to be 10:6, transferring the molten product obtained in the step (1) into a three-neck flask, adding 30mL of 2.0mol/L sodium dihydrogen phosphate solution, stirring uniformly, continuing adding 50mL of 2.0mol/L NaOH solution, stirring vigorously at 100 ℃ for 2h, and crystallizing for 6 h;
(3) and (3) after the crystallization in the step (2) is finished, taking out the product, filtering, washing a filter cake to be neutral, and drying for 3 hours at 80 ℃ to obtain the blast furnace slag-based hydroxyapatite-zeolite composite material. The microstructure, phase composition and elemental analysis of the prepared blast furnace slag-based hydroxyapatite-zeolite composite material are respectively shown in fig. 7, fig. 8 and fig. 9. The adsorption capacity test is carried out on the Mn-Mn composite material, and the results show that the Mn-Mn composite material respectively treats 50mg/L of Mn at room temperature2+，NH4 +，HPO4 2-The adsorption treatment is carried out, and the adsorption capacities are respectively as high as 26.58mg/g, 23.08mg/g and 25.32 mg/g.
The above embodiments are merely illustrative of the present invention and are not to be construed as limiting the invention. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that various combinations, modifications or equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and the technical solution of the present invention is covered by the claims of the present invention.
Claims (10)
1. A method for preparing a blast furnace slag-based composite material, comprising:
the method comprises the following steps: melting blast furnace slag and alkaline medium particles at high temperature to obtain a molten product;
step two: reacting the molten product with a phosphate solution, adding a NaOH solution, fully mixing, and crystallizing to obtain a crystallized product;
step three: and taking out the crystallized product, filtering, washing a filter cake to be neutral, and drying to obtain the blast furnace slag-based composite material.
2. The method of claim 1, wherein the first step comprises: the blast furnace slag and the alkaline medium particles are uniformly mixed according to the mass ratio of 1: 1.2-1: 1.3, and are melted at 500-600 ℃ for 60-120 min to obtain a molten product.
3. The method according to claim 1, wherein the second step comprises: controlling the Ca/P molar ratio of a reaction system to be 10:6, transferring the molten product into a reaction container, adding a proper amount of 2.0mol/L phosphate solution, stirring uniformly, continuing to add a proper amount of 2.0mol/L NaOH solution, stirring vigorously at 100 ℃ for 1-2 h, and crystallizing for 6-8 h.
4. The method according to claim 1, wherein in the third step, the drying treatment temperature is 60 to 80 ℃ and the time is 1 to 3 hours.
5. The method according to claim 1, wherein in the first step, the alkaline medium particles are any one of sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate and potassium carbonate.
6. The method according to claim 1, wherein in the second step, the phosphate solution is any one of potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, calcium dihydrogen phosphate, and calcium hydrogen phosphate.
7. The method of claim 1, wherein the blast furnace slag is steelmaking pig iron slag.
8. The method of claim 7The blast furnace slag comprises the following main components: SiO 2229.13％，CaO 47.08％，Al2O3 20.59％，MgO 1.11％。
9. A water treatment agent comprising the blast furnace slag-based composite material produced by the method according to any one of claims 1 to 8.
10. The water treatment agent according to claim 9, wherein the water treatment agent is used for adsorption of ammonium salts, heavy metals and phosphates.
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| CN112174153A (en) * | 2020-09-11 | 2021-01-05 | 重庆大学 | Method for preparing A-type zeolite by utilizing titanium-containing blast furnace slag |
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