CN110354797A - Porous nano iron oxide material and the preparation method and application thereof - Google Patents
Porous nano iron oxide material and the preparation method and application thereof Download PDFInfo
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- CN110354797A CN110354797A CN201810311491.XA CN201810311491A CN110354797A CN 110354797 A CN110354797 A CN 110354797A CN 201810311491 A CN201810311491 A CN 201810311491A CN 110354797 A CN110354797 A CN 110354797A
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- 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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- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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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
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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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
- 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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- 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
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The present invention relates to porous nanometer material fields, a kind of porous nano iron oxide material and the preparation method and application thereof is disclosed, the porous nano iron oxide material is mass ratio Fe: Cu: K: M1: M2: M3: S1=100 of the main composition of the material: (0-10): (0-10): (0-10): (0-10): (0-10): (0.1-30)；Wherein, the microscopic appearance of the material is at least one of rodlike, spindle, threadiness, needle-shaped, spherical and sheet, and the specific surface area of the material is 140-358m2/ g, average pore size 6-18nm.The invention also includes the preparation method of porous nano iron oxide material and applications.The tailing product that the present invention utilizes precipitated iron catalyst production process to generate, is prepared the environmentally friendly nano-iron oxide material of different-shape, porous structure, high-specific surface area, is with a wide range of applications.The method of the present invention equipment investment is low, simple and easy, turns waste into wealth, and greatly improves the added value for the waste material that traditional precipitated iron catalyst production process generates.
Description
Technical field
The present invention relates to porous nanometer material fields, and in particular to a kind of porous nano iron oxide material and its preparation side
Method and application.
Background technique
Fischer-Tropsch (F-T) synthesis is the core technology of ICL for Indirect Coal Liquefaction, is usually urged in the F-T synthesis such as iron-based or Supported Co of precipitating
Under the action of agent, by synthesis gas (CO+H2) be catalyzed for the purpose of reaction synthesizing liquid hydro carbons/wax class hydrocarbon products.Precipitate iron-based urge
Agent, because it is easy to get, adapts to the H of operation temperature and synthesis gas in raw material2/ CO is than wider, methane selectively is lower
Etc. advantage, be still the emphasis researched and developed in the industry.
Currently, precipitating iron-based F- T synthesis with the popularization and development of domestic indirect coal liquefaction (F- T synthesis) industry and urging
The production scale of agent increasingly increases.And a large amount of partial size is inevitably generated in the industrial processes of precipitated iron catalyst
How substandard product less than 50 μm efficiently utilizes these bad products, for Catalyst production for, no matter from
Environmental angle still all should not be underestimated in terms of promoting productivity effect.In recent years, with the inorganic nano material of special appearance
Material always is the hot spot that material supply section scholars study.Wherein, porous nano iron oxide can be used for removing sewage as adsorbent
The adsorbent of the anion such as middle phosphorus-containing compound also can be used as the scavenger of the hypertoxic metal ion such as Gr.
For example, prior art CN1248486A discloses a kind of iron-rare earth element compound water treatment adsorbent and its preparation
Method, the iron-rare earth element compound water treatment adsorbent are by divalent, trivalent molysite (such as frerrous chloride, iron chloride or ferrous sulfate
Ferric sulfate etc.) and rare earth element salt (such as cerium salt lanthanum salt) react synthesis, the Mole percent of the three classes salt under alkaline condition
It is trivalent molysite 40-60%, divalent molysite 20-35%, rare earth element 10-35% than range.Above-mentioned three classes salt under normal temperature conditions,
PH value is to react in 7-11 alkaline solution, generates a kind of sediment, washs through deionized water, is made after dry.At the Compound Water
It manages adsorbent to be used in phosphorus-containing wastewater processing or drinking water treatment containing arsenic, compared with common activated alumina adsorbents, not
The adsorbance of phosphorus or arsenic under synthermal and different pH condition is significantly increased, and adsorption rate is obviously accelerated, and adsorbance
It is influenced by the variation of pH value small.But the preparation of the compound water treatment adsorbent need to prepare iron oxidation since the precipitating of material solution
Object adsorbent, preparation flow are long, it will generate large amount of sewage, and raw material is mostly to contain chlorine or sulphur.
CN1486783A discloses a kind of oxide of high activity iron adsorbent and preparation method thereof, oxide of high activity iron absorption
The preparation of agent is that (such as iron chloride, ferric nitrate or ferric sulfate, the molar concentration of aqueous solution are 0.2- by soluble trivalent inorganic molysite
1.5M), it is added to water soluble hydroxy polymer (polyvinyl alcohol, the mass concentration of aqueous solution are 0.1-2.0wt%) or water-soluble
In amido polymer (polyacrylamide, the mass concentration of aqueous solution are 0.1-2.0wt%) aqueous solution, stirring keeps it completely molten
The strong base solution that concentration is 1.0-10.0M is added in the case of stirring in solution, and the pH value of reaction solution is controlled 2.5~5.5
Between, obtain precipitated product, then by washing to precipitated product, dehydration, it is dry after obtain oxide of high activity iron adsorbent.
The preparation of the oxide of high activity iron adsorbent need to equally prepare ferriferous oxide adsorbent, preparation stream since the precipitating of material solution
Journey is long, it will generates large amount of sewage.
CN103272553A discloses a kind of for removing the preparation side of the magnetic Nano iron oxide adsorbent of arsenic in water body
Method, comprising the following steps: the first step mixes the aqueous solution of molysite aqueous solution and alkali, and iron hydroxide is made, is centrifugated
Afterwards, glacial acetic acid is added, and stirs until forming hydrated ferric oxide colloidal solution, second step is added organic molten into colloidal solution
Agent, hydrated ferric oxide react to form complex precipitate with organic solvent, dry after separation, roasting obtains the suction of magnetic Nano iron oxide
Attached dose.The preparation of the magnetic Nano iron oxide adsorbent need to equally prepare ferriferous oxide absorption since the precipitating of material solution
Agent, preparation flow is long, and preparation process is complicated, and can generate large amount of sewage.
CN105107480A discloses a kind of for adsorbing the hypertoxic mesoporous FeOOH adsorbent of pollutant Cr (6+)
Preparation method is to mix the ethanol solution three of inorganic molysite solution, urea liquid and Pluronic triblock copolymer, stirs
It is heated in drying box after mixing uniformly, obtains the suspension of mesoporous FeOOH-Pluronic triblock copolymer, at room temperature
The suspension is successively centrifuged, and distills water washing, ethanol washing and vacuum drying, is made.The mesoporous FeOOH is inhaled
Attached dose of preparation need to equally prepare ferriferous oxide adsorbent since the precipitating of material solution, and preparation flow is long, and preparation process is multiple
It is miscellaneous, and large amount of sewage can be generated.
To sum up, the preparation of ferriferous oxide adsorbent is substantially prepares since the precipitating of material solution, and operating process is long,
Preparation process is complicated, and raw material, which is related to complexity and difficult compound and preparation process itself, will generate large amount of sewage etc. and lack
Point.
Summary of the invention
The purpose of the invention is to overcome the prior art to exist to prepare since the precipitating of material solution, operating process
Long, the problems such as preparation process is complicated and generates large amount of sewage, provides a kind of porous nano iron oxide material and its preparation side
Method and application.
To achieve the goals above, one aspect of the present invention provides a kind of porous nano iron oxide material, the master of the material
Mass ratio Fe: Cu: K: M1: M2: M3: S1=100 to be formed: (0-10): (0-10): (0-10): (0-10): (0-10):
(0.1-30), wherein M1 is selected from least one of Li, Na, Ba, Ca and Sr；M2 be selected from Zr, Gr, Y, Ti, Mn, Mo, V, Co,
At least one of Ni and Zn；M3 is selected from least one of Nd, Ce, Ld, Ta and Sm；S1 is selected from SiO2、Al2O3、TiO2With
ZrO2At least one of；Wherein, the microscopic appearance of the material is rodlike, spindle, in threadiness, needle-shaped, spherical and sheet
At least one, the specific surface area of the material are 140-358m2/ g, average pore size 6-18nm.
Second aspect of the present invention provides a kind of preparation method of porous nano iron oxide material, comprising the following steps:
(1) precipitated iron catalyst tailing, organic additive and water are mixed, obtains mixture；
(2) in confined conditions, the mixture that step (1) obtains is heated；
(3) liquid is pumped after cooling down or being depressured, and remaining solid material is dried.
Third aspect present invention provides a kind of porous nano iron oxide material prepared by the above method.
Fourth aspect present invention provides a kind of porous nano iron oxide material and applies in the treatment of waste water.
Compared with prior art, the invention has the following advantages:
1) the tailing product generated using precipitated iron catalyst production process is prepared with different-shape feature, more
The environmentally friendly nano-iron oxide material of pore structure, high-specific surface area.Compared with raw catalyst tailing, Nanoscale Iron of the present invention
The specific surface area of oxide material at least improves 40% or more.
2) present invention improvement after precipitated iron catalyst tailing according to its shape characteristic, adsorption capacity, magnetic strength and
The speciality such as photoinduction, are with a wide range of applications, for example, as high-efficiency adsorbent, it is pollution-free, it is environmentally friendly, to phosphorous
Compound etc. or the great adsorbing and removing function of the water pollutants such as other toxic heavy metals.
3) the method for the present invention equipment investment is low, simple and easy, turns waste into wealth, and greatly improves traditional precipitated iron catalyst
The added value for the waste material that production process generates.
Detailed description of the invention
Fig. 1 is the rodlike porous nano ferriferous oxide electron microscope of embodiment 1.
Fig. 2 is 2 spindle porous nano ferriferous oxide electron microscope of embodiment.
Fig. 3 is the linear porous nano ferriferous oxide electron microscope of embodiment 3.
Fig. 4 is the needle-shaped porous nano ferriferous oxide electron microscope of embodiment 4.
Fig. 5 is the spherical porous nano ferriferous oxide electron microscope of embodiment 5.
Fig. 6 is the flake porous nano-iron oxide electron microscope of embodiment 6.
Fig. 7 is 1 porous nano ferriferous oxide XRD diagram of embodiment.
Fig. 8 is 2 porous nano ferriferous oxide XRD diagram of embodiment.
Fig. 9 is 3 porous nano ferriferous oxide XRD diagram of embodiment.
Figure 10 is 4 porous nano ferriferous oxide XRD diagram of embodiment.
Figure 11 is 5 porous nano ferriferous oxide XRD diagram of embodiment.
Figure 12 is 6 porous nano ferriferous oxide XRD diagram of embodiment.
On the basis of Figure 13 is 1 porous nano ferriferous oxide HRTEM Fig. 1 of embodiment, to the calibration knot of crystal phase structure progress
Fruit figure.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of porous nano iron oxide material, mass ratio Fe: Cu: K: M1 of the main composition of the material
: M2: M3: S1=100: (0-10): (0-10): (0-10): (0-10): (0-10): (0.1-30), wherein M1 be selected from Li, Na,
At least one of Ba, Ca and Sr, M2 are selected from least one of Zr, Gr, Y, Ti, Mn, Mo, V, Co, Ni and Zn, and M3 is selected from
At least one of Nd, Ce, Ld, Ta and Sm, S1 are selected from SiO2、Al2O3、TiO2And ZrO2At least one of；Wherein, the material
Microscopic appearance be at least one of rodlike, spindle, threadiness, needle-shaped, spherical and sheet, the specific surface area of the material is
140-358m2/ g, average pore size 6-18nm.
The present invention is the improved high-specific surface area for obtaining different-shape feature, porous structure of precipitated iron catalyst tailing
Environmentally friendly nano-iron oxide material.Compared with raw catalyst tailing, the specific surface of nano-iron oxide material of the present invention
Product at least improves 40% or more.
In the present invention, the crystal phase composition of porous nano iron oxide material is controllable.According to the present invention, described porous
The crystal phase composition of nano-iron oxide material is mainly α-Fe2O3。
The present invention provides a kind of preparation method of porous nano iron oxide material, comprising the following steps:
(1) precipitated iron catalyst tailing, organic additive and water are mixed, obtains mixture；
(2) in confined conditions, the mixture that step (1) obtains is heated；
(3) liquid is pumped after cooling down or being depressured, and remaining solid material is dried.
The present invention creates a high-temperature high-voltage reaction environment using water and organic additive as reaction dissolvent, by heating, from
And the chemical reaction different from normality occurs for induction system.The method of the present invention is not only efficient, at low cost, and can by temperature,
Pressure effectively to control porous nano iron oxide material shape characteristic, crystal phase composition, pore-size distribution etc..The method of the present invention equipment
Invest it is low, it is simple and easy, turn waste into wealth, greatly improve the additional of the waste material that traditional precipitated iron catalyst production process generates
Value.
In the present invention, in step (1), the precipitated iron catalyst tailing: water: the mass ratio of organic additive is 1:
(5-50): (0.0001-0.1) is conducive to the formation of porous nano iron oxide material.
In the present invention, precipitated iron catalyst tailing is from a wealth of sources, in step (1), the precipitated iron catalyst tailing
Tailing is spray-dried for precipitated iron catalyst, precipitated iron catalyst tabletting is crushed tailing, precipitated iron catalyst sieves tailing and urges
At least one of any cake form tailing generated in agent production process.
In the present invention, precipitated iron catalyst tailing be the partial size that is generated in the industrial processes of precipitated iron catalyst not
Qualified products, in step (1), the partial size of the precipitated iron catalyst tailing is less than 50 μm.
According to the present invention, in step (1), molar ratio Fe: Cu: K: M1 of the main composition of the precipitated iron catalyst tailing
: M2: M3: S1=100: (0-10): (0-10): (0-10): (0-10): (0-10): (0.1-30), wherein M1 be selected from Li, Na,
At least one of Ba, Ca and Sr, M2 are selected from least one of Zr, Gr, Y, Ti, Mn, Mo, V, Co, Ni and Zn, and M3 is selected from
At least one of Nd, Ce, Ld, Ta and Sm, S1 are selected from SiO2、Al2O3、TiO2And ZrO2At least one of.
In the present invention, to organic additive type, there is no particular limitation, and can be various conventional in this field has
Machine additive, as long as can play the role of pore-creating, in step (1), the organic additive is organic acid, Organic Alcohol, has
At least one of machine aldehyde and organic ketone.Under preferable case, the organic acid is acetic acid, ethanedioic acid or propionic acid, and Organic Alcohol is first
Alcohol or ethyl alcohol, organic aldehyde are formaldehyde or acetaldehyde, and organic ketone is acetone or propanedione.
In the present invention, by temperature, the controllability of pressure, it can reach effectively control porous nano iron oxide material shape
Looks feature, crystal phase composition, pore-size distribution etc..In step (2), at 100-450 DEG C, pressure is controlled in 0.1- for the temperature control
6MPa, heating time are 0.1-48 hours.
Under preferable case, at 150-250 DEG C, pressure is controlled in 0.5-3MPa, heating time 1-36 for the temperature control
Hour.
The present invention provides a kind of porous nano iron oxide material prepared by the above method.
The present invention provides a kind of porous nano iron oxide material and applies in the treatment of waste water, described useless under preferable case
Water is the waste water of phosphorus-containing compound or toxic heavy metal.
Porous nano iron oxide material of the present invention is great to water pollutants such as phosphorus-containing compound etc. or toxic heavy metals
Adsorbing and removing function, and it is pollution-free, it is environmental-friendly.It is demonstrated experimentally that phosphorus compound or toxic heavy metal removal efficiency are up to 99%.
The present invention will be described in detail by way of examples below.In following embodiment:
The specific surface area and pore volume of precipitated iron catalyst tailing and porous nano iron oxide material: specific surface area uses
The measurement of BET specific surface method, pore volume are measured using low-temperature nitrogen adsorption method.
The constituent content of precipitated iron catalyst tailing: analysis measurement is carried out using X-ray fluorescence spectrometer (XRF).
The microstructure of nano material: it is tested using HRTEM.
The crystal phase structure of nano material: being tested using XRD or is demarcated by HRTEM test result.
Embodiment 1
Precipitated iron catalyst spray drying whirlwind tailing is analyzed using X-ray fluorescence spectrometer (XRF), it is known that
Precipitated iron catalyst is spray-dried the main composition of whirlwind tailing and content is Fe: Cu: K: Na: SiO2=100: 3.0: 5.0:
0.4:0.3:23.5.It weighs 20.0g precipitated iron catalyst spray drying whirlwind tailing to be placed in pressure vessel, 200mL is added and goes
Ionized water then weighs 0.05g methanol and acetic acid, is added in tailing, then that said vesse is closed, is placed in air dry oven
In, 220 DEG C, pressure 1.5MPa are heated to, constant temperature 32 hours, after cooling down, baking oven is taken out, draws all liquid phases with suction pipe,
Remaining wet catalyst fines are put into baking oven, and drying overnight obtains porous nano iron oxide material.
Porous nano iron oxide material sample is tested through HRTEM, as shown in Figure 1.As shown in Figure 1, porous nano iron oxygen
Compound material morphology be it is rodlike, diameter is about 3-5nm, and length is about 20-110nm.Porous nano iron oxide material sample warp
XRD test and the calibration of HRTEM test result, as shown in Fig. 7,13.By Fig. 7,13 it is found that porous nano iron oxide material crystalline substance
Phase structure is a-Fe2O3。
Embodiment 2
Precipitated iron catalyst spray drying whirlwind tailing is analyzed using x-ray fluorescence component analysis instrument (XRF), it is known that
Precipitated iron catalyst is spray-dried the main composition of whirlwind tailing and content is Fe: Cu:K: Mn: Ca: Ce: SiO2=100: 5.0:
7.0:6.0:1.5:3.0:15.5.It weighs 20.0g precipitated iron catalyst spray drying whirlwind tailing to be placed in pressure vessel, be added
200mL deionized water then weighs 0.05g ethyl alcohol and 0.01g acetone, is added in tailing, then that said vesse is closed, sets
In air dry oven, 180 DEG C, pressure 1.1MPa are heated to, constant temperature 32 hours, after cooling down, baking oven is taken out, is inhaled with suction pipe
All liquid phases are taken, remaining wet catalyst fines are put into baking oven, and drying overnight obtains porous nano iron oxide material.
Porous nano iron oxide material sample is tested through HRTEM, as shown in Figure 2.As shown in Figure 2, porous nano iron oxygen
Compound material morphology is spindle, and wide about 3-5nm, thickness is about 1-2nm, and length is about 20-110nm.Porous nano iron oxygen
Compound material sample is tested through XRD, as shown in Figure 8.As shown in Figure 8, the crystal phase structure of porous nano iron oxide material is a-
Fe2O3。
Embodiment 3
Precipitated iron catalyst tabletting is crushed tailing and is analyzed using x-ray fluorescence component analysis instrument (XRF), it is known that precipitating
Iron catalyst tabletting is crushed the main composition of tailing and content is Fe: Cu: K: Li: Nd: Zr: SiO2=100: 1.0: 3.0: 0.3:
2.0:4.5:25.It weighs the broken tailing of 20.0g precipitated iron catalyst tabletting to be placed in pressure vessel, 200mL deionized water is added,
Then 0.05g ethyl alcohol and 0.01g acetone are weighed, is added in tailing, it is then that said vesse is closed, it is placed in air dry oven
In, 250 DEG C, pressure 0.7MPa are heated to, constant temperature 24 hours, after cooling down, baking oven is taken out, draws all liquid phases with suction pipe,
Remaining wet catalyst fines are put into baking oven, and drying overnight obtains porous nano iron oxide material.
Porous nano iron oxide material sample is tested through HRTEM, as shown in Figure 3.From the figure 3, it may be seen that porous nano iron oxygen
Compound material morphology is threadiness, and diameter is about 2-5nm, and length is about 20-120nm.Porous nano iron oxide material sample warp
XRD test, as shown in Figure 9.As shown in Figure 9, the crystal phase structure of porous nano iron oxide material is a-Fe2O3。
Embodiment 4
Porous nano iron oxide material is prepared according to the method for embodiment 1, unlike, precipitated iron catalyst tailing is
Precipitated iron catalyst sieves tailing, is heated to 450 DEG C, pressure 3.0MPa, constant temperature 1.0 hours.
Porous nano iron oxide material sample is tested through HRTEM, as shown in Figure 4.As shown in Figure 4, porous nano iron oxygen
Compound material morphology be it is needle-shaped, it is wide about 2-5nm, thickness is about 1-3nm, and length is about 20-100nm.The oxidation of porous nano iron
Object material sample is tested through XRD, as shown in Figure 10.As shown in Figure 10, the crystal phase structure of porous nano iron oxide material is a-
Fe2O3。
Embodiment 5
Porous nano iron oxide material is prepared according to the method for embodiment 1, unlike, 260 DEG C are heated to, pressure is
1.5MPa, constant temperature 0.1 hour.
Porous nano iron oxide material sample is tested through HRTEM, as shown in Figure 5.As shown in Figure 5, porous nano iron oxygen
Compound material morphology be it is spherical, diameter is about 5-16nm.Porous nano iron oxide material sample is tested through XRD, such as Figure 11 institute
Show.As shown in Figure 11, the crystal phase structure of porous nano iron oxide material is a-Fe2O3。
Embodiment 6
Porous nano iron oxide material is prepared according to the method for embodiment 1, unlike, 100 DEG C are heated to, pressure is
0.8MPa, constant temperature 48 hours.
Porous nano iron oxide material sample is tested through HRTEM, as shown in Figure 6.It will be appreciated from fig. 6 that porous nano iron oxygen
Compound material morphology is sheet, and wide about 2-6nm, thickness is about 0.5-3nm, and length is about 10-130nm.Porous nano iron oxygen
Compound material sample is tested through XRD, as shown in figure 12.As shown in Figure 12, the crystal phase structure of porous nano iron oxide material is
a-Fe2O3。
Comparative example 1
Catalyst tailing is same as Example 1, prepares porous nano iron oxide material according to the method for embodiment 1, no
It is same, it is added without deionized water, only adds 0.05g methanol and acetic acid, iron oxide material obtained.
Comparative example 2
Catalyst tailing is same as Example 1, prepares porous nano iron oxide material according to the method for embodiment 1, no
It is same, 500 DEG C, pressure 3.0MPa are heated to, iron oxide material obtained.
Comparative example 3
Catalyst tailing is same as Example 1, prepares porous nano iron oxide material according to the method for embodiment 1, no
It is same, 90 DEG C, pressure 1.5MPa are heated to, iron oxide material obtained.
Test case
(1) the porous nano iron oxide material and embodiment 1-6 and comparative example of embodiment 1-6 and comparative example 1-3 preparation
The marcotexture parameter for the precipitated iron catalyst tailing that 1-3 is selected is measured using cryogenic nitrogen physical absorption BET specific surface method.Its
Measurement result is shown in Tables 1 and 2.
Table 1
Table 2
It can be seen that embodiment 1-6 by the Comparative result of Tables 1 and 2 and prepare porous nano iron oxide material BET ratio
Surface area at least improves 40% or more.
Application examples 1
The application of porous nano iron oxide material, porous nano iron oxide material 1.0g prepared by embodiment 1 are thrown
Enter into the waste water of 1.0L phosphorus-containing compound, wherein the waste strength (being metering with the quality of phosphorus) of phosphorus-containing compound is 0.2g/
L, the removal rate for measuring phosphorus compound is 99.7%.
Application examples 2
The application of porous nano iron oxide material, porous nano iron oxide material 1.0g prepared by embodiment 1 are thrown
Enter into waste water of the 1.0L containing arsenic, wherein the waste strength containing arsenic is 0.4g/L, and the removal rate for measuring arsenic is 99.95%.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of porous nano iron oxide material, which is characterized in that mass ratio Fe: Cu: K: M1 of the main composition of the material:
M2: M3: S1=100: (0-10): (0-10): (0-10): (0-10): (0-10): (0.1-30), wherein M1 be selected from Li, Na,
At least one of Ba, Ca and Sr, M2 are selected from least one of Zr, Gr, Y, Ti, Mn, Mo, V, Co, Ni and Zn, and M3 is selected from
At least one of Nd, Ce, Ld, Ta and Sm, S1 are selected from SiO2、Al2O3、TiO2And ZrO2At least one of；Wherein, the material
Microscopic appearance be at least one of rodlike, spindle, threadiness, needle-shaped, spherical and sheet, the specific surface area of the material is
140-358m2/ g, average pore size 6-18nm.
2. porous nano iron oxide material according to claim 1, which is characterized in that the porous nano ferriferous oxide
The crystal phase composition of material is mainly α-Fe2O3。
3. a kind of preparation method of porous nano iron oxide material according to claim 1 or 2, which is characterized in that packet
Include following steps:
(1) precipitated iron catalyst tailing, organic additive and water are mixed, obtains mixture；
(2) in confined conditions, the mixture that step (1) obtains is heated；
(3) liquid is pumped after cooling down or being depressured, and remaining solid material is dried.
4. according to the method described in claim 3, it is characterized in that, the precipitated iron catalyst tailing: water: having in step (1)
The mass ratio of machine additive is 1: (5-50): (0.0001-0.1).
5. the method according to claim 3 or 4, which is characterized in that in step (1), the precipitated iron catalyst tailing is
Precipitated iron catalyst is spray-dried tailing, precipitated iron catalyst tabletting is crushed tailing, precipitated iron catalyst sieves tailing and catalysis
At least one of cake form tailing generated in agent production process；
Preferably, the partial size of the precipitated iron catalyst tailing is less than 50 μm.
6. the method according to claim 3 or 4, which is characterized in that in step (1), the precipitated iron catalyst tailing
Mass ratio Fe: Cu: K: M1: M2: M3: S1=100 mainly formed: (0-10): (0-10): (0-10): (0-10): (0-10):
(0.1-30)；Wherein, M1 is selected from least one of Li, Na, Ba, Ca and Sr, M2 be selected from Zr, Gr, Y, Ti, Mn, Mo, V, Co,
At least one of Ni and Zn, M3 are selected from least one of Nd, Ce, Ld, Ta and Sm, and S1 is selected from SiO2、Al2O3、TiO2With
ZrO2At least one of.
7. the method according to claim 3 or 4, which is characterized in that in step (1), the organic additive be organic acid,
At least one of Organic Alcohol, organic aldehyde and organic ketone；
Preferably, the organic acid is acetic acid, ethanedioic acid or propionic acid, and Organic Alcohol is methanol or ethyl alcohol, and organic aldehyde is formaldehyde or second
Aldehyde, organic ketone are acetone or propanedione.
8. the method according to claim 3 or 4, which is characterized in that in step (2), the temperature control is in 100-450
DEG C, in 0.1-6MPa, heating time is 0.1-48 hours for pressure control；
Preferably, the temperature control is at 150-250 DEG C, and in 0.5-3MPa, heating time is 1-36 hours for pressure control.
9. a kind of porous nano iron oxide material that the method according to any one of claim 3-8 is prepared.
10. according to claim 1, the answering in the treatment of waste water of porous nano iron oxide material described in any one of 2 and 9
With；
Preferably, the waste water is the waste water of phosphorus-containing compound or toxic heavy metal.
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