CN111545165A - Double-hole environment functional material prepared from high-pressure entrained flow gasifier coarse slag and preparation method and application thereof - Google Patents
Double-hole environment functional material prepared from high-pressure entrained flow gasifier coarse slag and preparation method and application thereof Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 113
- 239000000463 material Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
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- 238000003756 stirring Methods 0.000 claims abstract description 24
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 22
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- 239000000203 mixture Substances 0.000 claims description 83
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000011148 porous material Substances 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 229910052782 aluminium Inorganic materials 0.000 claims description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 25
- 229910052710 silicon Inorganic materials 0.000 claims description 25
- 239000010703 silicon Substances 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 229910052593 corundum Inorganic materials 0.000 claims description 17
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- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 17
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- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 14
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- 239000012265 solid product Substances 0.000 claims description 13
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- 238000006243 chemical reaction Methods 0.000 claims description 12
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- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
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- 230000007935 neutral effect Effects 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
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- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- 230000003213 activating effect Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- 239000013335 mesoporous material Substances 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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- 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
- B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
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- 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
- B01J20/041—Oxides or hydroxides
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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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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
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
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- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- B01J2220/00—Aspects relating to sorbent materials
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- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
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- C01P2006/16—Pore diameter
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/16—Nitrogen compounds, e.g. ammonia
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Abstract
The invention discloses a method for preparing a double-hole environment functional material by using coarse slag of a high-pressure entrained flow gasifier, which comprises the following steps: the method is characterized in that coarse slag generated by a high-pressure entrained flow gasification furnace of a coal chemical industry base is taken as a raw material, and the raw material is subjected to grinding and screening, molar ratio adjustment, stirring, aging, crystallization, washing and drying, and ammonia nitrogen adsorption. The method simplifies the preparation process of the double-hole environment functional material, reduces the production energy consumption, saves water resources, reduces secondary pollution, reduces the cost, is suitable for wide popularization, effectively recycles the coarse slag of the high-pressure entrained-flow bed gasification furnace, and has wide application prospect. The obtained double-hole environment functional material has excellent physical and chemical adsorption performance, is used for adsorbing ammonia nitrogen in wastewater, and has excellent effect of removing ammonia nitrogen in coal chemical industry wastewater. The invention not only solves the huge environmental pressure of waste accumulation, but also reduces the treatment cost of enterprises, achieves the resource utilization of waste, and realizes the purpose of treating wastes with processes of wastes against one another.
Description
The technical field is as follows:
the invention relates to the technical field of double-hole environment functional materials, in particular to a double-hole environment functional material prepared by using coarse slag of a high-pressure entrained flow gasifier, and a preparation method and application thereof.
Background art:
with the great influence of global climate change on human living environment, the clean and efficient utilization of coal is very important. At present, clean coal in China mainly adopts coal gasification technology and the like, the technology is widely applied to the aspect of coal chemical industry, but the problems of solid waste and water pollution generated by the technology are more and more serious, and waste residue of a high-pressure entrained flow gasifier is the most main solid waste generated by the coal gasification technology. Because the carbon content of the waste residue of the high-pressure entrained flow gasifier is high, the waste residue can not be used as building materials; and the material contains a large amount of trace elements, particularly harmful elements, is very easy to pollute underground water and soil, and cannot be used as an underground backfill material. At present, no good treatment method exists, only high-standard anti-seepage treatment can be carried out on the ground for landfill, and the method is greatly different from the system utilization of the fly ash. This treatment not only occupies land resources, but also creates a tremendous environmental pressure and also brings high transportation and treatment costs to the enterprises. Therefore, realizing the zero emission of the coal gasification technology and finding a way for recycling the waste residue of the high-pressure entrained flow gasifier are very important.
The waste slag of the high-pressure entrained flow bed gasification furnace is water-containing slag discharged from the bottom of the gasification furnace after coal particles are subjected to processes of melting, chilling, condensation and the like under the high-temperature and high-pressure condition of the gasification furnace in the high-temperature entrained flow bed gasification process. The chemical composition of the material is mainly SiO2、Al2O3、CaO、Fe2O3And MgO, which can be used as raw material for synthesizing environment pore functional material. The preparation process for synthesizing the porous material by using the waste residue reported at present usually needs to add an expensive tableThe surfactant is used as a template agent, an aluminum source is added to adjust the silicon-aluminum ratio, a large amount of water is used, and high-temperature roasting crystallization is needed to obtain the single-phase double-hole (1.5nm and 3.5nm) functional material with high crystallinity, so that the existing method has the defects of high production cost, complex process, easiness in generating secondary pollution, high energy consumption and the like.
Therefore, it is very important to research a waste residue recycling technology of a high-pressure entrained-flow bed gasification furnace with simple process, low energy consumption, small secondary pollution and low cost.
The invention content is as follows:
the invention aims to provide a double-pore environment functional material prepared from high-pressure entrained-flow bed gasifier coarse slag, a preparation method and application thereof, which can be used for effectively recycling high-pressure entrained-flow bed gasifier waste slag, namely, the coarse slag in the high-pressure entrained-flow bed gasifier waste slag is used as a main raw material to prepare the double-pore environment functional material and apply the double-pore environment functional material to absorb ammonia nitrogen in wastewater, thereby simplifying the preparation process of the double-pore environment functional material, reducing the production energy consumption, saving water resources, reducing secondary pollution, lowering cost and being suitable for wide popularization.
The invention discloses a method for preparing a double-hole environment functional material by using coarse slag of a high-pressure entrained flow gasifier, which comprises the following steps:
(1) drying, crushing, grinding and screening the coarse slag of the high-pressure entrained flow bed gasification furnace, and selecting a part with the particle size of less than 200 meshes to obtain coarse slag powder of the gasification furnace;
(2) adding NaOH solution and deionized water into the coarse slag powder of the gasification furnace obtained in the step (1) to adjust the molar ratio to obtain a mixture, wherein the molar ratio in the mixture is SiO2∶Al2O3∶Na2O∶H2O is x: 1.0: 3.5-7.5: 50-200, wherein the molar ratio of silicon to aluminum is the initial molar ratio of silicon to aluminum of the raw material;
(3) uniformly stirring the mixture obtained in the step (2) at room temperature, then transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and aging the mixture for 24-72 hours at the temperature of 20-30 ℃;
(4) placing the mixture aged in the step (3) in an oven at the temperature of 105-130 ℃, and keeping the temperature for 6-48 h to grow crystals;
(5) and (4) filtering the mixture obtained in the step (4), washing the obtained solid product with deionized water to be neutral, and drying to obtain the double-hole environment functional material.
Preferably, the high-pressure entrained flow gasifier coarse slag of the step (1) comprises the following components in percentage by weight: 53.4 wt% of silicon dioxide, 17.2 wt% of aluminum oxide, 11.2 wt% of iron oxide, 10.1 wt% of calcium oxide and 1.33 wt% of sodium oxide, wherein SiO is2∶Al2O3The molar ratio of (A) to (B) is 5.2: 1.0.
Preferably, in the step (1), the coarse slag of the high-pressure entrained-flow bed gasification furnace is dried for 10-15 hours at 100-110 ℃, then is crushed for 10-20 seconds in a swing type crusher, is then ground in a planetary ball mill for 30-60 min, and is selected by a vibrating screen machine to obtain the coarse slag powder of the gasification furnace, wherein the particle size of the coarse slag is less than 200 meshes.
Preferably, the planetary ball mill of step (1) has a weight ratio of grinding balls to raw materials of 5: 1, and the grinding balls include grinding balls with a diameter of 15mm and grinding balls with a diameter of 10mm, and the weight ratio of the grinding balls to the raw materials is grinding ballsDiameter of 15mmGrinding ballDiameter of 10mm＝3∶2。
Preferably, the concentration of the NaOH solution in the step (2) is 5 mol/L.
Preferably, in the step (3), the mixture obtained is stirred at room temperature for 1-3 hours by magnetic force, and the stirring speed is 100-200 r/min.
Preferably, in the step (5), the solid product obtained by filtering is dried for 5-10 h at 100-110 ℃.
The invention also discloses a double-hole environment functional material prepared by using the coarse slag of the high-pressure entrained flow gasifier.
Preferably, the molecular composition of the double-hole environment functional material is Na3.6Al3.6Si12.4O32·H2O, the double-pore diameter of the double-pore environment functional material is 1.5nm and 3.5nm, and the specific surface area is 130-175 m2(g) the average adsorption pore diameter is 5-7 nm.
The invention also discloses application of the double-hole environment functional material, namely application of the double-hole environment functional material in adsorption of ammonia nitrogen in wastewater.
The invention has the beneficial effects that:
(1) the cost is low: firstly, the main raw materials are coarse slag in waste slag of a high-pressure entrained flow gasifier in a coal chemical industry base in western China, and the raw materials belong to solid waste, so that the cost is low and the waste treatment effect is achieved; secondly, a silicon source and an aluminum source are not needed to be added in the synthesis process, and according to the content of silicon and aluminum in the raw material, the silicon and aluminum raw material is effectively saved, and the cost is reduced; in addition, no surfactant is used as a template agent in the synthesis process, so that the cost is further reduced;
(2) the process is simple: the environment functional material with a double-hole structure is prepared by using the high-pressure entrained flow gasifier coarse slag and sodium hydroxide as raw materials through a one-step method, and the environment functional material is simple in process and strong in implementability;
(3) and (3) water resource saving: only a small amount of water is needed to be added in the synthesis process, so that the water consumption and water pollution are reduced to the minimum;
(5) energy consumption is saved: in the synthesis process, a single-phase high-crystallinity double-pore environment functional material can be formed without high-temperature calcination, so that the energy consumption and the cost are further reduced;
the method for preparing the double-hole environment functional material by using the coarse slag of the high-pressure entrained flow gasifier comprises the following steps: coarse slag generated by a high-pressure entrained flow gasifier of a coal chemical industry base is taken as a raw material, and the raw material is subjected to grinding and screening, molar ratio adjustment, stirring, aging, crystallization, washing, drying and ammonia nitrogen adsorption. The method is controlled by a preparation process, the coarse slag of the high-pressure entrained flow bed gasification furnace is used as a main raw material to prepare the double-hole environment functional material, industrial waste is used as the raw material in the preparation process, only a small amount of water is needed, the preparation method is controlled according to the properties of the raw material, no surfactant is needed to be added, no new silicon-aluminum source is needed to be added, high-temperature roasting is not needed, and low-cost and low-pollution recycling of industrial solid waste is realized. The method simplifies the preparation process of the double-hole environment functional material, reduces the production energy consumption, saves water resources, reduces secondary pollution, reduces the cost, is suitable for wide popularization, effectively recycles the coarse slag of the high-pressure entrained-flow bed gasification furnace, and has wide application prospect.
The double-hole environment functional material prepared by using the high-pressure entrained flow gasifier coarse slag has a special double-hole (1.5nm and 3.5nm) structure, has excellent physical and chemical adsorption properties, is used for adsorbing ammonia nitrogen in wastewater, and has an excellent effect of removing the ammonia nitrogen in coal chemical industry wastewater.
In conclusion, the invention well utilizes the characteristic of the initial silicon-aluminum ratio in the coarse slag, and the material with special double-hole environment function is prepared by the control of the preparation method, thereby not only solving the huge environmental pressure of waste accumulation, but also reducing the treatment cost of enterprises, achieving the resource utilization of waste and realizing the purpose of treating waste by waste.
Description of the drawings:
FIG. 1 is a diagram of a prepared double-pore environment functional material obtained by the preparation method of the invention;
FIG. 2 is a pore size distribution diagram of the raw slag of the high-pressure entrained flow gasifier as such and the prepared dual-pore environment functional material;
FIG. 3 is an XRD diagram of the original coarse slag of the high-pressure entrained-flow bed gasification furnace and the prepared dual-pore environment functional material;
FIG. 4 is a scanning electron microscope image of a high pressure entrained flow gasifier coarse slag feed;
FIG. 5 is a scanning electron microscope image of the dual-pore environment functional material prepared by the present invention.
The specific implementation mode is as follows:
firstly, the main raw materials: coarse slag of high-pressure entrained-flow bed gasification furnace
The coarse slag of the high-pressure entrained flow gasifier adopted in the embodiment comprises the following components in percentage by weight: 53.4 wt% of silicon dioxide, 17.2 wt% of aluminum oxide, 11.2 wt% of iron oxide, 10.1 wt% of calcium oxide and 1.33 wt% of sodium oxide, wherein SiO is2∶Al2O3The molar ratio of (A) to (B) is 5.2: 1.0.
Secondly, a method for preparing the double-hole environment functional material by using the coarse slag of the high-pressure entrained flow gasifier comprises the following steps:
(1) drying the coarse slag of the high-pressure entrained flow bed gasification furnace for 10-15 h at 100-110 ℃, then crushing the coarse slag in a swing type crusher for 10-20 s, then placing the coarse slag in a planetary ball mill for grinding for 30-60 min, and selecting a part with the particle size of less than 200 meshes through a vibrating screen machine to obtain coarse slag powder of the gasification furnace, wherein:
the weight ratio of the ball materials in the planetary ball mill is 5: 1 of grinding balls to raw materials, the grinding balls comprise grinding balls with the diameter of 15mm and grinding balls with the diameter of 10mm, and the weight ratio of the grinding balls to the grinding balls isDiameter of 15mmGrinding ballDiameter of 10mm＝3∶2；
(2) Adding NaOH solution with the concentration of 5mol/L and deionized water into the coarse slag powder of the gasification furnace obtained in the step (1) to adjust the molar ratio to obtain a mixture, wherein the molar ratio in the mixture is SiO2∶Al2O3∶Na2O∶H2O is x: 1.0: 3.5-7.5: 50-200, wherein the molar ratio of silicon to aluminum is the initial molar ratio of silicon to aluminum of the raw material;
(3) magnetically stirring the mixture obtained in the step (2) at room temperature for 1-3 hours at a stirring speed of 100-200 r/min, then transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and aging the mixture for 24-72 hours at 20-30 ℃;
(4) placing the mixture aged in the step (3) in an oven at the temperature of 105-130 ℃, and keeping the temperature for 6-48 h to grow crystals;
(5) filtering the mixture obtained in the step (4), washing the obtained solid product with deionized water to be neutral, and drying at the temperature of 100-110 ℃ for 5-10 h to obtain the double-hole environment functional material, wherein the molecular composition of the double-hole environment functional material is Na3.6Al3.6Si12.4O32·H2O, the double apertures are 1.5nm and 3.5nm, and the specific surface area is 130-175 m2(g) the average adsorption pore diameter is 5-7 nm.
Thirdly, application of the double-hole environment functional material:
the double-hole environment functional material is applied to adsorbing ammonia nitrogen in wastewater, and is thrown into the wastewater containing the ammonia nitrogen according to the amount of 20g/L, and is vibrated for 3 hours at the room temperature of 25 ℃ in a water bath constant temperature oscillator at the rotating speed of 180 r/min.
And fourthly, a performance detection method of the double-hole environment functional material:
preparing an ammonia nitrogen standard solution as simulated wastewater according to the national standard 'HJ 535-2009 ammonia nitrogen determination Nessler reagent spectrophotometry', wherein the concentration of ammonia nitrogen in the simulated wastewater is 100mg/L, putting 2g of the double-hole environment functional material prepared in the embodiment 1 into 100mL of the simulated wastewater, oscillating the simulated wastewater in an air constant temperature oscillator for 3h at a rotating speed of 180r/min, and determining the removal rate of the ammonia nitrogen by using an ultraviolet visible spectrophotometer.
Fifthly, the principle of the invention is as follows:
the preparation principle comprises the following steps: after the coarse slag of the high-pressure entrained-flow bed gasification furnace is fully mixed with NaOH solution, SiO to be reacted is formed on the surface of the coarse slag2And Al2O3And activating molecules, and enabling the two molecules to interact to promote the active ingredients in the coarse slag of the high-pressure entrained flow gasifier to fall off from the surfaces of the particles. When the alkali solution is heated, the effective component of the unit cell grid is changed into OH-The Si-O-Al, Si-O-Si and Al-O-Al bonds on the surface of the particles are broken to form new Al (OH)4 -Equipotential ions cause the surface of the particles to be negatively charged, so that a layer of Na is attached to the periphery of the solid particles in the solution under the electrostatic action+. Furthermore, active SiO2And Al2O3With Na+The reaction generates hydrated sodium aluminosilicate gel which covers the surface of the coarse slag of the high-pressure entrained flow gasifier, thus hindering the permeation and diffusion of active components and reducing the diffusion speed of active molecules passing through the coating layer. At this stage, Na in the system+Constantly gather on the coarse sediment surface of high-pressure entrained flow gasifier, the change of silicon-aluminum ratio leads to the continuous formation of crystal nucleus in the gel layer, appears complicated orderly latticed channel structure, is favorable to the diffusion of inlayer molecule for silicate congeals the crystallization, and along with the extension of time, the crystal particle on the coarse sediment surface of high-pressure entrained flow gasifier has finally formed stable diplopore environment function material structure.
(II) adsorption experiment principle: the adsorption of the double-hole environment functional material to ammonia nitrogen mainly depends on electrostatic adsorption capacity and ion exchange performance. The electrostatic adsorption is caused by the fact that a plurality of cations exist in crystal lattices of the double-hole environment functional material, and part of the structure has negative charges, so that the double-hole environment functional material can be shapedForming a strong electric field and generating strong adsorption capacity. The ion exchange is due to NH4 +The diameter of the porous material is about 0.286nm, the aperture of the prepared double-pore environment functional material is 1.5nm and 3.5nm, and the adsorption average aperture is 5-7 nm, so that NH4 +Can easily penetrate through the channel and the hole of the double-hole environment functional material and Na in the internal crystal lattice+、Ca2+When cations are exchanged, the ammonia nitrogen concentration in the wastewater is reduced, and secondly, the high-concentration ammonia nitrogen solution can provide more exchange substances and form larger concentration difference with the surface of the double-hole environment functional material, so that NH is promoted4 +Exchange with cations in the material.
Example 1:
the method for preparing the double-hole environment functional material by using the coarse slag of the high-pressure entrained flow gasifier comprises the following steps:
(1) drying the coarse slag of the high-pressure entrained flow gasifier at 100 ℃ for 15h, then crushing the coarse slag in a swing type crusher for 10s, then placing the coarse slag in a planetary ball mill for grinding for 60min, and selecting a part with the particle size of less than 200 meshes through a vibrating screen machine to obtain coarse slag powder of the gasifier; wherein
The weight ratio of the ball materials in the planetary ball mill is 5: 1 of grinding balls to raw materials, the grinding balls comprise grinding balls with the diameter of 15mm and grinding balls with the diameter of 10mm, and the weight ratio of the grinding balls to the grinding balls isDiameter i5mmGrinding ballDiameter of 10mm＝3∶2。
(2) Adding NaOH solution with the concentration of 5mol/L and deionized water into the coarse slag powder of the gasification furnace obtained in the step (1) to adjust the molar ratio to obtain a mixture, wherein the molar ratio in the mixture is SiO2∶Al2O3∶Na2O∶H2O is 5.2: 1.0: 5.0: 100, wherein the molar ratio of silicon to aluminum is the initial molar ratio of silicon to aluminum;
(3) magnetically stirring the mixture obtained in the step (2) at room temperature for 1h at the stirring speed of 200r/min, then transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and aging the mixture for 24h at 23 ℃;
(4) placing the mixture aged in the step (3) in an oven at 105 ℃, and keeping the temperature for 12 hours to grow crystals;
(5) the mixture obtained in step (4) was filtered, and then the obtained solid product was washed to neutrality with deionized water and dried at 100 ℃ for 5 hours to obtain sample 1.
Example 2:
the method for preparing the double-hole environment functional material by using the coarse slag of the high-pressure entrained flow gasifier comprises the following steps:
(1) drying the coarse slag of the high-pressure entrained flow gasifier at 110 ℃ for 10h, then crushing the coarse slag in a swing type crusher for 20s, then placing the coarse slag in a planetary ball mill for grinding for 30min, and selecting a part with the particle size of less than 200 meshes through a vibrating screen machine to obtain coarse slag powder of the gasifier; wherein
The weight ratio of the ball materials in the planetary ball mill is 5: 1 of grinding balls to raw materials, the grinding balls comprise grinding balls with the diameter of 15mm and grinding balls with the diameter of 10mm, and the weight ratio of the grinding balls to the grinding balls isDiameter of 15mmGrinding ballDiameter of 10mm＝3∶2。
(2) Adding NaOH solution with the concentration of 5mol/L and deionized water into the coarse slag powder of the gasification furnace obtained in the step (1) to adjust the molar ratio to obtain a mixture, wherein the molar ratio in the mixture is SiO2∶Al2O3∶Na2O∶H2O is 5.2: 1.0: 3.5: 100, wherein the molar ratio of silicon to aluminum is the initial molar ratio of silicon to aluminum;
(3) magnetically stirring the mixture obtained in the step (2) at room temperature for 3 hours at the stirring speed of 100r/min, then transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and aging the mixture for 24 hours at the temperature of 28 ℃;
(4) placing the mixture aged in the step (3) in an oven at the temperature of 130 ℃, and keeping the temperature for 24 hours to grow crystals;
(5) the mixture obtained in step (4) was filtered, and then the resulting solid product was washed to neutrality with deionized water and dried at 110 ℃ for 5 hours to obtain sample 2.
Example 3:
the method for preparing the double-hole environment functional material by using the coarse slag of the high-pressure entrained flow gasifier comprises the following steps:
(1) drying the coarse slag of the high-pressure entrained flow gasifier at 105 ℃ for 12h, then crushing the coarse slag in a swing type crusher for 15s, then placing the coarse slag in a planetary ball mill for grinding for 45min, and selecting a part with the particle size of less than 200 meshes through a vibrating screen machine to obtain coarse slag powder of the gasifier; wherein
The weight ratio of the ball materials in the planetary ball mill is 5: 1 of grinding balls to raw materials, the grinding balls comprise grinding balls with the diameter of 15mm and grinding balls with the diameter of 10mm, and the weight ratio of the grinding balls to the grinding balls isDiameter of 15mmGrinding ballDiameter of 10mm＝3∶2。
(2) Adding NaOH solution with the concentration of 5mol/L and deionized water into the coarse slag powder of the gasification furnace obtained in the step (1) to adjust the molar ratio to obtain a mixture, wherein the molar ratio in the mixture is SiO2∶Al2O3∶Na2O∶H2O is 5.2: 1.0: 5.0: 50, wherein the molar ratio of silicon to aluminum is the initial molar ratio of silicon to aluminum;
(3) magnetically stirring the mixture obtained in the step (2) at room temperature for 2 hours at the stirring speed of 150r/min, then transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and aging the mixture for 24 hours at the temperature of 25 ℃;
(4) placing the mixture aged in the step (3) in an oven at the temperature of 105 ℃, and keeping the temperature for 24 hours to grow crystals;
(5) the mixture obtained in step (4) was filtered, and then the resulting solid product was washed to neutrality with deionized water and dried at 105 ℃ for 6 hours to obtain sample 3.
Example 4:
the method for preparing the double-hole environment functional material by using the coarse slag of the high-pressure entrained flow gasifier comprises the following steps:
(1) drying the coarse slag of the high-pressure entrained flow gasifier at 105 ℃ for 12h, then crushing the coarse slag in a swing type crusher for 15s, then placing the coarse slag in a planetary ball mill for grinding for 30min, and selecting a part with the particle size of less than 200 meshes through a vibrating screen machine to obtain coarse slag powder of the gasifier; wherein
The weight ratio of the ball materials in the planetary ball mill is 5: 1 of grinding balls to raw materials, and the grinding balls comprise grinding balls with the diameter of 15mmGrinding ball and grinding ball with diameter of 10mm, the weight ratio of the grinding ball to the grinding ballDiameter of 15mmGrinding ballDiameter of 10mm＝3∶2。
(2) Adding NaOH solution with the concentration of 5mol/L and deionized water into the coarse slag powder of the gasification furnace obtained in the step (1) to adjust the molar ratio to obtain a mixture, wherein the molar ratio in the mixture is SiO2∶Al2O3∶Na2O∶H2O is 5.2: 1.0: 5.0: 150, wherein the molar ratio of silicon to aluminum is the initial molar ratio of silicon to aluminum;
(3) magnetically stirring the mixture obtained in the step (2) at room temperature for 2 hours at the stirring speed of 150r/min, then transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and aging the mixture for 48 hours at 25 ℃;
(4) placing the mixture aged in the step (3) in a drying oven at the temperature of 105 ℃, and keeping the temperature for 48 hours to grow crystals;
(5) the mixture obtained in step (4) was filtered, and then the resulting solid product was washed to neutrality with deionized water and dried at 105 ℃ for 6 hours to obtain sample 4.
Example 5:
the method for preparing the double-hole environment functional material by using the coarse slag of the high-pressure entrained flow gasifier comprises the following steps:
(1) drying the coarse slag of the high-pressure entrained flow gasifier at 102 ℃ for 14h, then crushing the coarse slag in a swing type crusher for 12s, then placing the coarse slag in a planetary ball mill for grinding for 55min, and selecting a part with the particle size of less than 200 meshes through a vibrating screen machine to obtain coarse slag powder of the gasifier; wherein
The weight ratio of the ball materials in the planetary ball mill is 5: 1 of grinding balls to raw materials, the grinding balls comprise grinding balls with the diameter of 15mm and grinding balls with the diameter of 10mm, and the weight ratio of the grinding balls to the grinding balls isDiameter of 15mmGrinding ballDiameter of 10mm＝3∶2。
(2) Adding NaOH solution with the concentration of 5mol/L and deionized water into the coarse slag powder of the gasification furnace obtained in the step (1) to adjust the molar ratio to obtain a mixture, wherein the molar ratio in the mixture is SiO2∶Al2O3∶Na2O∶H2O＝5.2: 1.0: 7.5: 150, wherein the molar ratio of silicon to aluminum is the initial molar ratio of silicon to aluminum of the raw material;
(3) magnetically stirring the mixture obtained in the step (2) at room temperature for 2 hours at the stirring speed of 150r/min, then transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and aging the mixture for 72 hours at the temperature of 20 ℃;
(4) placing the mixture aged in the step (3) in an oven at the temperature of 105 ℃, and keeping the temperature for 36 hours to grow crystals;
(5) the mixture obtained in step (4) was filtered, and then the resulting solid product was washed to neutrality with deionized water and dried at 104 ℃ for 9 hours to obtain sample 5.
Example 6:
the method for preparing the double-hole environment functional material by using the coarse slag of the high-pressure entrained flow gasifier comprises the following steps:
(1) drying the coarse slag of the high-pressure entrained flow gasifier at 104 ℃ for 13h, then crushing the coarse slag in a swing type crusher for 14s, then placing the coarse slag in a planetary ball mill for grinding for 50min, and selecting a part with the particle size of less than 200 meshes through a vibrating screen machine to obtain coarse slag powder of the gasifier; wherein
The weight ratio of the ball materials in the planetary ball mill is 5: 1 of grinding balls to raw materials, the grinding balls comprise grinding balls with the diameter of 15mm and grinding balls with the diameter of 10mm, and the weight ratio of the grinding balls to the grinding balls isDiameter of 15mmGrinding ballDiameter of 10mm＝3∶2。
(2) Adding NaOH solution with the concentration of 5mol/L and deionized water into the coarse slag powder of the gasification furnace obtained in the step (1) to adjust the molar ratio to obtain a mixture, wherein the molar ratio in the mixture is SiO2∶Al2O3∶Na2O∶H2O is 5.2: 1.0: 5.0: 200, wherein the molar ratio of silicon to aluminum is the initial molar ratio of silicon to aluminum;
(3) magnetically stirring the mixture obtained in the step (2) at room temperature for 2.5 hours at the stirring speed of 150r/min, then transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and aging the mixture for 36 hours at 23 ℃;
(4) placing the mixture aged in the step (3) in an oven at the temperature of 115 ℃, and keeping the temperature for 24 hours to grow crystals;
(5) the mixture obtained in step (4) was filtered, and then the resulting solid product was washed to neutrality with deionized water and dried at 107 ℃ for 7 hours to obtain sample 6.
Example 7:
the method for preparing the double-hole environment functional material by using the coarse slag of the high-pressure entrained flow gasifier comprises the following steps:
(1) drying the coarse slag of the high-pressure entrained flow gasifier at 106 ℃ for 12h, then crushing the coarse slag in a swing type crusher for 16s, then placing the coarse slag in a planetary ball mill for grinding for 40min, and selecting a part with the particle size of less than 200 meshes through a vibrating screen machine to obtain coarse slag powder of the gasifier; wherein
The weight ratio of the ball materials in the planetary ball mill is 5: 1 of grinding balls to raw materials, the grinding balls comprise grinding balls with the diameter of 15mm and grinding balls with the diameter of 10mm, and the weight ratio of the grinding balls to the grinding balls isDiameter of 15mmGrinding ballDiameter of 10mm＝3∶2。
(2) Adding NaOH solution with the concentration of 5mol/L and deionized water into the coarse slag powder of the gasification furnace obtained in the step (1) to adjust the molar ratio to obtain a mixture, wherein the molar ratio in the mixture is SiO2∶Al2O3∶Na2O∶H2O is 5.2: 1.0: 4.0: 150, wherein the molar ratio of silicon to aluminum is the initial molar ratio of silicon to aluminum;
(3) magnetically stirring the mixture obtained in the step (2) at room temperature for 2 hours at the stirring speed of 150r/min, then transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and aging the mixture at 25 ℃ for 36 hours;
(4) placing the mixture aged in the step (3) in an oven at the temperature of 125 ℃, and keeping the temperature for 6 hours to grow crystals;
(5) the mixture obtained in step (4) was filtered, and then the resulting solid product was washed to neutrality with deionized water and dried at 102 ℃ for 8 hours to obtain sample 7.
Example 8:
the method for preparing the double-hole environment functional material by using the coarse slag of the high-pressure entrained flow gasifier comprises the following steps:
(1) drying the coarse slag of the high-pressure entrained flow gasifier at 108 ℃ for 11h, then crushing the coarse slag in a swing type crusher for 18s, then placing the coarse slag in a planetary ball mill for grinding for 35min, and selecting a part with the particle size of less than 200 meshes through a vibrating screen machine to obtain coarse slag powder of the gasifier; wherein
The weight ratio of the ball materials in the planetary ball mill is 5: 1 of grinding balls to raw materials, the grinding balls comprise grinding balls with the diameter of 15mm and grinding balls with the diameter of 10mm, and the weight ratio of the grinding balls to the grinding balls isDiameter of 15mmGrinding ballDiameter of 10mm＝3∶2。
(2) Adding NaOH solution with the concentration of 5mol/L and deionized water into the coarse slag powder of the gasification furnace obtained in the step (1) to adjust the molar ratio to obtain a mixture, wherein the molar ratio in the mixture is SiO2∶Al2O3∶Na2O∶H2O is 5.2: 1.0: 6.0: 125, wherein the molar ratio of silicon to aluminum is the initial molar ratio of silicon to aluminum;
(3) magnetically stirring the mixture obtained in the step (2) at room temperature for 2 hours at the stirring speed of 150r/min, then transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and aging the mixture for 48 hours at 25 ℃;
(4) placing the mixture aged in the step (3) in an oven at the temperature of 130 ℃, and keeping the temperature for 24 hours to grow crystals;
(5) the mixture obtained in step (4) was filtered, and then the resulting solid product was washed to neutrality with deionized water and dried at 105 ℃ for 8 hours to obtain sample 8.
Table 1: EXAMPLES Performance characterization of the samples obtained
| Item | Sample (I) | Specific surface area (m)2/g) | Average pore diameter of adsorption (nm) | Ammonia nitrogen removal (%) |
| Example 1 | Sample 1 | 161.06 | 5.58 | 92.67 |
| Example 2 | Sample 2 | 155.97 | 6.13 | 90.88 |
| Example 3 | Sample 3 | 139.84 | 6.52 | 87.54 |
| Example 4 | Sample No. 4 | 173.56 | 5.22 | 93.33 |
| Example 5 | Sample No. 5 | 142.66 | 5.89 | 88.43 |
| Example 6 | Sample No. 6 | 131.71 | 6.97 | 85.29 |
| Example 7 | Sample 7 | 133.49 | 6.71 | 86.66 |
| Example 8 | |
141.26 | 6.18 | 87.12 |
As can be seen from Table 1, the specific surface area of the double-hole environment functional material prepared by using the coarse slag of the high-pressure entrained-flow bed gasification furnace is 130-175 m2The adsorption average pore diameter is 5-7 nm, the ammonia nitrogen removal rate is greater than 85%, the ammonia nitrogen removal rate can reach more than 93%, namely the obtained double-pore environment functional material has excellent physical and chemical adsorption performance, and the removal effect of the double-pore environment functional material on ammonia nitrogen in coal chemical industry wastewater is excellent.
As can be seen from FIG. 1, the dual-pore environment functional material prepared by the present invention using the high-pressure entrained-flow gasifier coarse slag is yellowish brown powder.
As can be seen from FIG. 2, the dual-pore environment functional material prepared by the high-pressure entrained flow gasifier coarse slag has an IV-type isotherm (relative pressure range is 0.45-0.99) of an H3 hysteresis loop, which is a typical characteristic of mesoporous materials, and has a special dual-pore (1.5nm and 3.5nm) structure.
As can be seen from FIG. 3, no obvious crystalline phase appears in the raw slag of the high-pressure entrained flow gasifier, wherein the silicon-aluminum and other substances mainly exist in an amorphous state, and the double-hole environment functional material prepared by the high-pressure entrained flow gasifier raw slag of the invention has an obvious characteristic peak of the mesoporous functional material, single crystalline phase and high crystallinity.
As can be seen from FIGS. 4 and 5, the raw material of the high-pressure entrained-flow bed gasifier coarse slag has a flaky or granular structure with irregular shape and nonuniform size, while the double-hole environment functional material prepared by the high-pressure entrained-flow bed gasifier coarse slag has an obvious and regular rectangular prismatic crystal structure, and shows 4-7 μm cauliflower-shaped aggregates which are formed by anisotropic growth of rectangular crystals with the average diameter of less than 1 μm.
Claims (10)
1. A method for preparing a double-hole environment functional material by using coarse slag of a high-pressure entrained flow gasifier is characterized by comprising the following steps:
(1) drying, crushing, grinding and screening the coarse slag of the high-pressure entrained flow bed gasification furnace, and selecting a part with the particle size of less than 200 meshes to obtain coarse slag powder of the gasification furnace;
(2) adding NaOH solution and deionized water into the coarse slag powder of the gasification furnace obtained in the step (1) to adjust the molar ratio to obtain a mixture, wherein the molar ratio in the mixture is SiO2∶Al2O3∶Na2O∶H2O is x: 1.0: 3.5-7.5: 50-200, wherein the molar ratio of silicon to aluminum is the initial molar ratio of silicon to aluminum of the raw material;
(3) uniformly stirring the mixture obtained in the step (2) at room temperature, then transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and aging the mixture for 24-72 hours at the temperature of 20-30 ℃;
(4) placing the mixture aged in the step (3) in an oven at the temperature of 105-130 ℃, and keeping the temperature for 6-48 h to grow crystals;
(5) and (4) filtering the mixture obtained in the step (4), washing the obtained solid product with deionized water to be neutral, and drying to obtain the double-hole environment functional material.
2. The method for preparing a dual-pore environment functional material using the high-pressure entrained-flow gasifier coarse slag according to claim 1,the high-pressure entrained flow gasifier coarse slag of the step (1) comprises the following components in percentage by weight: 53.4 wt% of silicon dioxide, 17.2 wt% of aluminum oxide, 11.2 wt% of iron oxide, 10.1 wt% of calcium oxide and 1.33 wt% of sodium oxide, wherein SiO is2∶Al2O3The molar ratio of (A) to (B) is 5.2: 1.0.
3. The method for preparing a dual-pore environment functional material from the high-pressure entrained-flow gasifier coarse slag according to claim 1, wherein in the step (1), the high-pressure entrained-flow gasifier coarse slag is dried at 100-110 ℃ for 10-15 h, then is crushed in a swing type crusher for 10-20 s, is then put in a planetary ball mill for grinding for 30-60 min, and is selected by a vibrating screen machine to obtain the gasifier coarse slag powder material with the particle size of less than 200 meshes.
4. The method for preparing a dual pore environment functional material using the coarse slag of the high pressure entrained-flow gasifier as claimed in claim 3, wherein the planetary ball mill of step (1) has a ball material weight ratio of 5: 1, and the grinding balls include grinding balls with a diameter of 15mm and grinding balls with a diameter of 10mm, and the weight ratio of the grinding balls to the raw material is grinding ballsDiameter of 15mmGrinding ballDiameter of 10mm＝3∶2。
5. The method for preparing a dual-pore environment functional material using the high-pressure entrained-flow gasifier coarse slag according to claim 1, wherein the concentration of the NaOH solution in the step (2) is 5 mol/L.
6. The method for preparing the dual-pore environment functional material by using the coarse slag of the high-pressure entrained-flow gasifier as claimed in claim 1, wherein the mixture obtained in the step (3) is stirred at room temperature for 1-3 h by magnetic force, and the stirring speed is 100-200 r/min.
7. The method for preparing the dual-pore environment functional material by using the high-pressure entrained-flow gasifier coarse slag according to claim 1, wherein the solid product obtained by filtering in the step (5) is dried at 100-110 ℃ for 5-10 h.
8. A dual-pore environment functional material prepared by the preparation method of any one of claims 1 to 7.
9. The dual-pore environment functional material according to claim 8, wherein the molecular composition thereof is Na3.6Al3.6Si12.4O32·H2O with double apertures of 1.5nm and 3.5nm and a specific surface area of 130-175 m2(g) the average adsorption pore diameter is 5-7 nm.
10. Use of the dual-pore environment functional material according to claim 8 or 9, characterized in that it is used for adsorbing ammonia nitrogen in wastewater.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002179424A (en) * | 2000-12-11 | 2002-06-26 | Zeotec:Kk | Method of manufacturing artificial zeolite and method of manufacturing foamed perlite |
| CN101723397A (en) * | 2009-11-27 | 2010-06-09 | 抚顺矿业集团有限责任公司 | Method for preparing zeolite molecular sieve by using oil shale residues |
| KR20130045978A (en) * | 2011-10-27 | 2013-05-07 | 한국지질자원연구원 | Enhancement of carbonation efficiency from the blast furnace slag |
| CN103084143A (en) * | 2013-01-28 | 2013-05-08 | 安徽工程大学 | Two-pore zeolite microsphere and preparation method thereof |
| CN107159172A (en) * | 2017-05-31 | 2017-09-15 | 东北大学 | The preparation method of zeolite denitrogenation dephosphorizing agent and zeolite denitrogenation dephosphorizing agent |
| CN107381524A (en) * | 2017-08-15 | 2017-11-24 | 中国神华能源股份有限公司 | The method and NaP molecular sieves of NaP molecular sieves are prepared using white clay as raw material |
| CN110813265A (en) * | 2019-10-21 | 2020-02-21 | 宁夏大学 | Preparation method and application of β -CD/ZIF-8/PMMA composite cationic dye solid-phase extraction adsorbent |
-
2020
- 2020-04-23 CN CN202010375429.4A patent/CN111545165A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002179424A (en) * | 2000-12-11 | 2002-06-26 | Zeotec:Kk | Method of manufacturing artificial zeolite and method of manufacturing foamed perlite |
| CN101723397A (en) * | 2009-11-27 | 2010-06-09 | 抚顺矿业集团有限责任公司 | Method for preparing zeolite molecular sieve by using oil shale residues |
| KR20130045978A (en) * | 2011-10-27 | 2013-05-07 | 한국지질자원연구원 | Enhancement of carbonation efficiency from the blast furnace slag |
| CN103084143A (en) * | 2013-01-28 | 2013-05-08 | 安徽工程大学 | Two-pore zeolite microsphere and preparation method thereof |
| CN107159172A (en) * | 2017-05-31 | 2017-09-15 | 东北大学 | The preparation method of zeolite denitrogenation dephosphorizing agent and zeolite denitrogenation dephosphorizing agent |
| CN107381524A (en) * | 2017-08-15 | 2017-11-24 | 中国神华能源股份有限公司 | The method and NaP molecular sieves of NaP molecular sieves are prepared using white clay as raw material |
| CN110813265A (en) * | 2019-10-21 | 2020-02-21 | 宁夏大学 | Preparation method and application of β -CD/ZIF-8/PMMA composite cationic dye solid-phase extraction adsorbent |
Non-Patent Citations (1)
| Title |
|---|
| WENXIN JI ET AL.: "Green Synthesis Method and Application of NaP Zeolite Prepared by Coal Gasification Coarse Slag from Ningdong, China", 《APPLIED SCIENCES》 * |
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