CN109928431A - A kind of iron oxide and its synthetic method - Google Patents
A kind of iron oxide and its synthetic method Download PDFInfo
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Abstract
The present invention provides a kind of macroporous iron oxide and its synthetic method, and the constituent of the iron oxide is alpha-ferric oxide, has two-stage duct, intermediary hole most probable pore size is having a size of 15~25nm；The pore diameter range of macropore is 50~1500nm.The synthetic method includes pre-processing Beta molecular sieve；Then by Beta molecular sieve, ferric nitrate, carbohydrate and water mixing, stirring ultrasonic treatment；It is dried again and high-temperature process；Finally processing obtains macroporous iron oxide in aqueous slkali.The method of the present invention is without using expensive organic additive, the even aperture distribution of the macroporous iron oxide of preparation.
Description
Technical field
The invention belongs to porous inorganic materials to synthesize field, specifically a kind of macroporous iron oxide and its synthetic method.
Background technique
Iron oxide is a kind of cheap and easy to get, environmentally protective functional material, is protected in catalysis, magnetic apparatus, sensor, environment
The numerous areas such as shield, medical diagnosis and therapy, purification of water quality and pollution processing have broad application prospects.
CN102260542 discloses a kind of preparation method of three-dimensional ordered macroporous ferric oxide desulfurizer, which uses glue
Crystal template method prepares large pore material, using polystyrene microsphere glue crystal template as macropore template, then predecessor is filled in template
Gap in, finally remove template obtain three-dimensional ordered macroporous iron oxide.But template assemblies take long time, preparation cost mistake
It is high.
CN101723469 A discloses a kind of soft and hard double plate of three-dimensional ordered macroporous iron oxide for preparing mesoporous wall
Method, this method, by nine water ferric nitrates and soft template P123, are dissolved in dehydrated alcohol or anhydrous under room temperature, normal pressure and ultrasound condition
In methanol and anhydrous ethylene glycol mixture, then contained in the hard template PMMA microsphere of close packed array with mixed liquor infiltration
The mixed liquor of PMMA can be prepared by the three-dimensional with mesoporous wall of water chestnut square structure after suction filtration, drying and temperature-programmed calcination
Ordered big hole iron oxide.The patent is characterized in having used double-template, and one is glue crystal template, the other is soft template P123,
Its preparation cost is also excessively high.
CN102951687A discloses a kind of iron oxide mesoporous microsphere and preparation method thereof, first prepares containing before pore former
Liquid is driven, then precursor liquid is obtained into microsphere powder by spray drying granulation；Finally roasting obtains mesoporous iron oxide.It is used at
Hole agent is high molecular polymer.
CN101733102A discloses the preparation of ferric oxide multi-porous monolithic catalyst, discloses a kind of macroporous iron oxide
Preparation method.The patent is first using alkoxy silane as silicon source, using polyethylene glycol as macropore template, using ammonium hydroxide as mesoporous template
Agent first prepares bimodal porous silica entirety column template.Then by nitrate solution by monolithic silica column, finally with sodium hydroxide solution
Silica gel is dissolved, is obtained a kind of comprising macropore and mesoporous monolithic porous iron oxide.
In conjunction with above-mentioned analysis it is found that existing macropore or porous ferric oxide material preparation method are remained such as template assemblies
It takes long time, the problems such as preparation cost is high, be difficult to industrialized production, the pore size distribution of material is uneven, and physico-chemical property is poor.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of macroporous iron oxide and its synthetic method, provided by the invention
Macroporous iron oxide has macroporous structure abundant, and pore size distribution is uniform, and affiliated synthetic method is simple and easy, and production cost is low.
The present invention provides a kind of macroporous iron oxide, and the macroporous iron oxide has the feature that constituent is alpha-oxidation
Iron has two-stage duct, and intermediary hole most probable pore size is having a size of 15~25nm；The pore diameter range of macropore is 50~1500nm,
Macropore most probable pore size D is 60-1000nm, wherein the ratio that the macropore between 0.8D-1.2D accounts for entire macropore is greater than 60%.
In above-mentioned macroporous iron oxide, the macroporous iron oxide specific surface area is 50~150 m2/g。
The present invention provides a kind of synthetic method of macroporous iron oxide, and the method includes following contents:
(1) Beta molecular sieve is mixed with PhCOONa solution, is separated by solid-liquid separation after mixing, and to the solid being collected into
It is dried；
(2) the Beta molecular sieve for obtaining step (1), ferric nitrate, glucide and water are uniformly mixed；
(3) by the obtained dry materials of step (2) to moisture evaporating completely；
(4) solid material for obtaining step (3) is handled in nitrogen or inert atmosphere high temperature；
(5) solid material for obtaining step (4) is in the processing of air atmosphere high temperature；
(6) solid material that step (5) obtains is mixed with lye, in 100~200 DEG C of 1~10h of processing, then crosses washing, does
It is dry to obtain macroporous iron oxide.
In the method for the present invention, the crystalline size of the Beta molecular sieve is 70~1000nm, and the Beta molecular sieve can be with
The satisfactory commodity that purchase market is sold, can also be prepared according to existing method.
In the method for the present invention, the Beta molecular sieve can be prepared via a method which: by alkali source, silicon source, silicon source, water and
Template (TEAOH) is according to 3~8Na of molar ratio2O:40~100SiO2: A12O3: 800~1200H2The ratio of O:10~30TEAOH
Example is uniformly mixed, and is then charged into closed reactor 10~60h of crystallization at 100~180 DEG C, and last separating, washing is done
It is dry, obtain Beta molecular sieve.
In the above method, the inorganic base is sodium hydroxide；Silicon source be sodium aluminate, aluminum sulfate, aluminium chloride, in aluminum nitrate
One or more；Silicon source is White Carbon black and/or silica solution；Template is tetraethyl ammonium hydroxide.
In the above method, the crystallization temperature is 100~180 DEG C, and the reaction time is 10~60h, preferably reaction temperature
Degree is 105~160 DEG C, and the reaction time is 20~50h.
In the above method, wash to be washed with distilled water；The drying condition be processing 5 under the conditions of 100~150 DEG C~
15h handles 6~12h under the conditions of preferably 110~140 DEG C.
It further include a pre-treatment step (1A) before step (1), first by the Beta molecular sieve in the method for the present invention
Put into screening solution in, allow Beta molecular sieve screening solution in natural subsidence, when molecular sieve be deposited to screening liquid bottom when,
Screening liquid is divided into the sectionals such as several, such as is divided into n sectional, n value for greater than 1 odd number (value of n can be 3,
5, the odd numbers such as 7,9,11).If the crystal size of molecular sieve is relatively uniform, n value can take lesser numerical value, on the contrary then take biggish
Numerical value.When screening molecular sieve, it can according to need the molecular sieve for selecting different sections, preferably select the molecular sieve of bosom section
(when being such as divided into three parts, taking intermediate 1/3, when being divided into 5 parts, take intermediate 1/5), and the molecular sieve filtration filtered out is dry.
In the above method, the screening solution is any one of aqueous solution of propylene glycol, glycerin solution, the screening
The concentration of solution is 5~75wt%, preferably 10~70wt%；The mass ratio for screening solution and Beta molecular sieve is 1~10:1, excellent
Select 2~8:1.
In the method for the present invention, separation of solid and liquid described in step (1) arbitrarily may be implemented to be separated by solid-liquid separation for this field is existing
Technological means, such as using filtering, solid material is separated with liquid, the solid material do not have to wash directly is dried.
In the method for the present invention, step (1) sodium benzoate mass concentration is 2~20wt%, preferably 3~18wt%；Sodium benzoate
It is 1~10:1, preferably 2~8:1 that solution and solid matter liquid, which consolidate mass ratio,.
In the method for the present invention, drying condition described in step (2) is 5~15h of processing under the conditions of 100~150 DEG C, preferably
6~12h is handled under the conditions of 110~140 DEG C.
In the method for the present invention, Beta molecular sieve described in step (2), ferric nitrate, glucide, water mass ratio be
0.1~2:1:0.1~2:10~33, preferably 0.2~1:1:0.2~1:12~30.
In the method for the present invention, glucide described in step (2) includes one or more of sucrose, glucose.
In the method for the present invention, drying temperature described in step (3) is 100~150 DEG C.
In the method for the present invention, high-temperature process temperature described in step (4) is 300~900 DEG C, preferably 400~800 DEG C；
Calcining time is 1~10h, preferably 2~8h.
In the method for the present invention, high-temperature process temperature described in step (5) is 300~900 DEG C, preferably 400~800 DEG C；
Calcining time is 1~10h, preferably 2~8h.
In the method for the present invention, step (6) lye be one of solution such as sodium hydroxide, potassium hydroxide, lithium hydroxide or
Several, concentration of lye is 15~55wt%, preferably 20~50wt%；The mass ratio of the lye and solid material is 1~10:1, excellent
It is selected as 2~8:1.
In the method for the present invention, treatment temperature is 100~200 DEG C, preferably 120~180 DEG C in step (6)；Handle the time
For 1~10h, preferably 2~8h.
In the method for the present invention, washing described in step (6) is to be washed with distilled water；Drying condition described in step (6)
It is to handle 5~15h under the conditions of 100~150 DEG C, handles 6~12h under the conditions of preferably 110~140 DEG C.
In the method for the present invention, mixing described in step (1), step (2) and step (6) can use stirring, cut at a high speed
Any mode in cutting, be ultrasonically treated etc., is preferably mixed under ultrasound condition, when using ultrasonic treatment, when processing
Between be 10~60min, preferably 15~55min, the frequency of ultrasonic wave is 15KHz-10MHz, power is calculated as 20 by liquor capacity~
100W/L。
Macroporous iron oxide provided by the invention has macropore abundant, can be used as catalyst, adsorbent or other function materials
Material.
Compared with prior art, macroporous iron oxide provided by the invention and preparation method thereof has the advantage that
In preparation method of the present invention, it is put forward for the first time using Beta molecular sieve as hard template and is used to prepare in macroporous iron oxide.
In the method for the present invention, by more having after being handled Beta molecular sieve with sodium benzoate and in conjunction with being ultrasonically treated
Monodisperse status is preferably kept conducive to by Beta molecular sieve, is conducive to molecular sieve for precursor species and is adsorbed on its outer surface,
It can guarantee that molecular sieve is more uniform to be dispersed in precursor solution, avoid molecular sieve that reunion and molecular sieve and forerunner occurs
Body generation mutually separates.Solving can not prepare greatly when molecular sieve occurs to reunite and molecular sieve occurs and mutually separates with presoma
Hole iron oxide, the technical issues of can only obtain common ferric oxide particles.The Beta handled in the method for the present invention with sodium benzoate
Molecular sieve is that the aperture concentration degree of macroporous iron oxide that template is prepared is higher, and pore-size distribution is more uniform, separation field more
Add tool advantage, the screening of isolate can be finely controlled according to Nano grade.
The present invention adds glucide in presoma.During heat treatment, saccharide converted to be steamed for carbon dioxide and water
Vapour overflows, and the position that glycogen first occupies can be vacated and be formed mesoporous.And it is mixed since carbohydrate belongs to atomic level with ferric nitrate,
Therefore preparation is mesoporous highly uniform, and property is more uniform.
In preparation method of the present invention, since Beta molecular sieve compares the hard template of other types, template size can be by
It is accurately adjusted according to demand, repeatability is high, and production cost is low.
Detailed description of the invention
Fig. 1 is the SEM photograph for the macroporous iron oxide that embodiment 1 synthesizes.
Specific embodiment
It is described in detail below by preparation method of the specific embodiment to macroporous iron oxide of the present invention, but not office
It is limited to embodiment.
Embodiment 1
(1) it takes 0.36g sodium hydroxide to be dissolved in the TEAOH and 15 mL distilled water of 40 mL 25wt%, stirs 30 min.Then
0.7g sodium aluminate is added, stirs 20 min.It is slowly added 12g white carbon black again, stirs 30 min.It is then charged into closed reactor
In, 145 DEG C of 32 h of crystallization in baking oven.Then obtained product is washed with distilled water to neutrality, then in 120 DEG C of conditions
Lower dry 12h, obtains Beta molecular sieve.
(2) the Beta molecular sieve that step (1) obtains is put into the propylene glycol solution of 50 mL 50wt%, makes it naturally heavy
Drop, when molecular sieve is just deposited to bottom, takes out the solution of 1/3 part in the middle part of entire solution, filters, 120 DEG C of dry 10h.
(3) the Beta molecular sieve that step (2) obtains is mixed with the PhCOONa solution of 15mL 10wt%, is ultrasonically treated
The frequency of 20min, ultrasonic wave are 0.01MHz, and power is calculated as 20W/L by liquor capacity；Then by primary filtering, at 120 DEG C
Under the conditions of dry 12h.
(4) Beta molecular sieve, 1g ferric nitrate, 1g sucrose that 1g step (3) obtains are separately added into 20mL water, stirring is equal
It is even, it is ultrasonically treated 20min, the frequency of ultrasonic wave is 0.01MHz, and power is calculated as 20W/L by liquor capacity.
(5) the obtained substance of step (4) is dry until moisture evaporating completely at 120 DEG C.
(6) 500 DEG C of constant temperature handle 5h in the solid matter nitrogen for obtaining step (5)；Then in air at 500 DEG C of constant temperature
Manage 5h.
(7) substance that step (6) obtains is mixed with the NaOH solution of 5mL 40wt%, is fitted into closed reactor 150 DEG C
7h is handled, obtained product is then washed with distilled water to neutrality, then dry 12h under the conditions of 120 DEG C, obtains macropore
Iron oxide, number CL1.Gained sample is as shown in Figure 1, be macroporous iron oxide.
Embodiment 2
(1) it takes 0.27 g sodium hydroxide to be dissolved in TEAOH the and 20mL distilled water of 40 mL 25wt%, stirs 30 min.Then
0.7 g sodium aluminate is added, stirs 30 min.It is slowly added 17g white carbon black again, stirs 30 min.It is then charged into closed reactor
In, 162 DEG C of 20 h of crystallization in baking oven.Then obtained product is washed with distilled water to neutrality, then in 120 DEG C of conditions
Lower dry 12h, obtains Beta molecular sieve.
(2) the Beta molecular sieve that step (1) obtains is put into the glycerin solution of 82 mL 72wt%, makes it naturally heavy
Drop, when molecular sieve is just deposited to bottom, takes out the solution of 1/5 part in the middle part of entire solution, filters, 120 DEG C of dry 10h.
(3) the Beta molecular sieve that step (2) obtains is mixed with the PhCOONa solution of 5mL 18wt%, is ultrasonically treated
The frequency of 20min, ultrasonic wave are 12MHz, and power is calculated as 100W/L by liquor capacity；Then by primary filtering, in 120 DEG C of items
Dry 12h under part.
(4) Beta molecular sieve, 1g ferric nitrate, 1.8g sucrose that 1.8g step (3) obtains are separately added into 30mL water, are stirred
It mixes uniformly, is ultrasonically treated 20min, the frequency of ultrasonic wave is 11MHz, and power is calculated as 100W/L by liquor capacity.
(5) the obtained substance of step (4) is dry until moisture evaporating completely at 120 DEG C.
(6) 420 DEG C of constant temperature handle 8h in the solid matter nitrogen for obtaining step (5)；400 DEG C of constant temperature processing in air
8h。
(7) substance that step (6) obtains is mixed with the NaOH solution of 5mL 55wt%, is fitted into closed reactor 180 DEG C
2h is handled, obtained product is then washed with distilled water to neutrality, then dry 12h under the conditions of 120 DEG C, obtains macropore
Iron oxide, number CL2.
Embodiment 3
(1) it takes 0.8 g sodium hydroxide to be dissolved in the TEAOH and 10 mL distilled water of 40 mL 25wt%, stirs 30 min.Then
1.2 g sodium aluminates are added, stir 30 min.It is slowly added 12.6 g white carbon blacks again, stirs 30 min.It is then charged into closed anti-
It answers in kettle, 105 DEG C of 50 h of crystallization in baking oven.Then obtained product is washed with distilled water to neutrality, then 120
Dry 12h, obtains Beta molecular sieve under the conditions of DEG C.
(2) the Beta molecular sieve that step (1) obtains is put into the propylene glycol solution of 20 mL 10wt%, makes it naturally heavy
Drop, when molecular sieve is just deposited to bottom, takes out the solution of 1/7 part in the middle part of entire solution, filters, 120 DEG C of dry 10h.
(3) the Beta molecular sieve that step (2) obtains is mixed with the PhCOONa solution of 5mL 10wt%, is ultrasonically treated
The frequency of 20min, ultrasonic wave are 1.2MHz, and power is calculated as 50W/L by liquor capacity；Then by primary filtering, in 120 DEG C of items
Dry 12h under part.
(4) Beta molecular sieve, 1.2g ferric nitrate, 0.2g sucrose that 0.2g step (3) obtains are separately added into 25mL water,
It stirs evenly, is ultrasonically treated 20min, the frequency of ultrasonic wave is 1.2MHz, and power is calculated as 50W/L by liquor capacity.
(5) the obtained substance of step (4) is dry until moisture evaporating completely at 120 DEG C.
(6) 800 DEG C of constant temperature handle 2h in the solid matter nitrogen for obtaining step (5)；800 DEG C of constant temperature processing in air
2h。
(7) substance that step (6) obtains is mixed with the NaOH solution of 5.5mL 15wt%, is fitted into 120 in closed reactor
DEG C processing 8h, is then washed with distilled water to neutrality for obtained product, then dry 12h under the conditions of 120 DEG C, obtains big
Hole iron oxide, number CL3.
Embodiment 4
(1) it takes 0.4 g sodium hydroxide to be dissolved in the TEAOH and 15 mL distilled water of 25 mL 25wt%, stirs 30 min.Then
0.7 g sodium aluminate is added, stirs 30 min.It is slowly added 12 g white carbon blacks again, stirs 30 min.It is then charged into confined reaction
In kettle, 120 DEG C of 35 h of crystallization in baking oven.Then obtained product is washed with distilled water to neutrality, then in 120 DEG C of items
Dry 12h, obtains Beta molecular sieve under part.
(2) the Beta molecular sieve that step (1) obtains is put into the propylene glycol solution of 45 mL 70wt%, makes it naturally heavy
Drop, when molecular sieve is just deposited to bottom, takes out the solution of 1/3 part in the middle part of entire solution, filters, 120 DEG C of dry 10h.
(3) the Beta molecular sieve that step (2) obtains is mixed with the PhCOONa solution of 8mL 15wt%, is ultrasonically treated
The frequency of 20min, ultrasonic wave are 1.15MHz, and power is calculated as 36W/L by liquor capacity；Then by primary filtering, at 120 DEG C
Under the conditions of dry 12h.
(4) Beta molecular sieve, 1g ferric nitrate, 1.45g sucrose that 1g step (3) obtains are separately added into 20mL water, are stirred
It mixes uniformly, is ultrasonically treated 20min, the frequency of ultrasonic wave is 1.15MHz, and power is calculated as 36W/L by liquor capacity.
(5) the obtained substance of step (4) is dry until moisture evaporating completely at 120 DEG C.
(6) 500 DEG C of constant temperature handle 5h in the solid matter nitrogen for obtaining step (5)；500 DEG C of constant temperature processing in air
5h。
(7) substance that step (6) obtains is mixed with the NaOH solution of 8mL 55wt%, is fitted into closed reactor 150 DEG C
7h is handled, obtained product is then washed with distilled water to neutrality, then dry 12h under the conditions of 120 DEG C, obtains macropore
Iron oxide, number CL4.
Embodiment 5
(1) 8g commodity Beta molecular sieve is put (Catalyst Factory, Nankai Univ) to enter in the propylene glycol solution of 50 mL 50wt%, is allowed
Its natural subsidence takes out the solution of 1/3 part in the middle part of entire solution when molecular sieve is just deposited to bottom, filtering, and 120 DEG C
Dry 10h.
(2) the Beta molecular sieve that step (1) obtains is mixed with the PhCOONa solution of 15mL 15wt%, is ultrasonically treated
The frequency of 20min, ultrasonic wave are 0.95MHz, and power is calculated as 32W/L by liquor capacity；Then by primary filtering, at 120 DEG C
Under the conditions of dry 12h.
(3) Beta molecular sieve, 0.6g ferric nitrate, 1.3g sucrose that 0.7g step (2) obtains are separately added into 15mL water,
It stirs evenly, is ultrasonically treated 20min, the frequency of ultrasonic wave is 0.85MHz, and power is calculated as 36W/L by liquor capacity.
(4) the obtained substance of step (3) is dry until moisture evaporating completely at 120 DEG C.
(5) 500 DEG C of constant temperature handle 5h in the solid matter nitrogen for obtaining step (4)；500 DEG C of constant temperature processing in air
5h。
(6) substance that step (5) obtains is mixed with the NaOH solution of 3.5mL 40wt%, is fitted into 150 in closed reactor
DEG C processing 7h, is then washed with distilled water to neutrality for obtained product, then dry 12h under the conditions of 120 DEG C, obtains big
Hole iron oxide, number CL5.
Embodiment 6
(1) it takes 0.4 g sodium hydroxide to be dissolved in the TEAOH and 15 mL distilled water of 25 mL 25wt%, stirs 30 min.Then
0.7 g sodium aluminate is added, stirs 30 min.It is slowly added 12 g white carbon blacks again, stirs 30 min.It is then charged into confined reaction
In kettle, 120 DEG C of 35 h of crystallization in baking oven.Then obtained product is washed with distilled water to neutrality, then in 120 DEG C of items
Dry 12h, obtains Beta molecular sieve under part.
(2) the Beta molecular sieve that step (1) obtains is put into the propylene glycol solution of 45 mL 70wt%, makes it naturally heavy
Drop, when molecular sieve is just deposited to bottom, takes out the solution of 1/3 part in the middle part of entire solution, filters, 120 DEG C of dry 10h.
(3) Beta molecular sieve, 1g ferric nitrate, 1.45g sucrose that 1g step (2) obtains are separately added into 20mL water, are stirred
It mixes uniformly, is ultrasonically treated 20min, the frequency of ultrasonic wave is 1.15MHz, and power is calculated as 36W/L by liquor capacity.
(4) the obtained substance of step (3) is dry until moisture evaporating completely at 120 DEG C.
(5) 500 DEG C of constant temperature handle 5h in the solid matter nitrogen for obtaining step (4)；500 DEG C of constant temperature processing in air
5h。
(6) substance that step (5) obtains is mixed with the NaOH solution of 8mL 55wt%, is fitted into closed reactor 150 DEG C
7h is handled, obtained product is then washed with distilled water to neutrality, then dry 12h under the conditions of 120 DEG C, obtains macropore
Iron oxide, number are CL 6.
Embodiment 7
(1) it takes 0.4 g sodium hydroxide to be dissolved in the TEAOH and 15 mL distilled water of 25 mL 25wt%, stirs 30 min.Then
0.7 g sodium aluminate is added, stirs 30 min.It is slowly added 12 g white carbon blacks again, stirs 30 min.It is then charged into confined reaction
In kettle, 120 DEG C of 35 h of crystallization in baking oven.Then obtained product is washed with distilled water to neutrality, then in 120 DEG C of items
Dry 12h, obtains Beta molecular sieve under part.
(2) the Beta molecular sieve that step (1) obtains is mixed with the PhCOONa solution of 8mL 15wt%, is ultrasonically treated
The frequency of 20min, ultrasonic wave are 1.15MHz, and power is calculated as 36W/L by liquor capacity；Then by primary filtering, at 120 DEG C
Under the conditions of dry 12h.
(3) Beta molecular sieve, 1g ferric nitrate, 1.45g sucrose that 1g step (2) obtains are separately added into 20mL water, are stirred
It mixes uniformly, is ultrasonically treated 20min, the frequency of ultrasonic wave is 1.15MHz, and power is calculated as 36W/L by liquor capacity.
(4) the obtained substance of step (3) is dry until moisture evaporating completely at 120 DEG C.
(5) 500 DEG C of constant temperature handle 5h in the solid matter nitrogen for obtaining step (4)；500 DEG C of constant temperature processing in air
5h。
(6) substance that step (5) obtains is mixed with the NaOH solution of 8mL 55wt%, is fitted into closed reactor 150 DEG C
7h is handled, obtained product is then washed with distilled water to neutrality, then dry 12h under the conditions of 120 DEG C, obtains macropore
Iron oxide, number are CL 7.
Comparative example 1
1g ferric nitrate is added in 20mL water, is stirred evenly, 40min is ultrasonically treated, the frequency of ultrasonic wave is 0.01MHz, power
20W/L is calculated as by liquor capacity；120 DEG C of dryings are until moisture evaporating completely again；Then 500 DEG C of constant temperature handle 5h；Then with 5mL
The NaOH solution of 40wt% mixes, and is fitted into 150 DEG C of processing 7h in closed reactor, then by the distillation washing of obtained product
It washs to neutrality, then dry 12h under the conditions of 120 DEG C, obtains iron oxide, number CL8.
Comparative example 2
1g ferric nitrate and 1g sucrose are separately added into 20mL water, stirred evenly, 40min is ultrasonically treated, the frequency of ultrasonic wave is
0.01MHz, power are calculated as 20W/L by liquor capacity；120 DEG C of dryings are until moisture evaporating completely again；Then 500 DEG C of perseverances in air
Temperature processing 5h；Then it is mixed with the NaOH solution of 5mL 40wt%, 150 DEG C of processing 7h in closed reactor is fitted into, then by gained
To product be washed with distilled water under the conditions of neutrality, then 120 DEG C dry 12h, obtain iron oxide, number CL9.
Comparative example 3
1g ferric nitrate and 1g sucrose are separately added into 20mL water, stirred evenly, 40min is ultrasonically treated, the frequency of ultrasonic wave is
0.01MHz, power are calculated as 20W/L by liquor capacity；120 DEG C of dryings are until moisture evaporating completely again；Then 500 DEG C of perseverances in nitrogen
Temperature processing 5h；500 DEG C of constant temperature handle 5h in air；Then it mixes, is fitted into closed reactor with the NaOH solution of 5mL 40wt%
Then obtained product is washed with distilled water under the conditions of neutrality, then 120 DEG C and dries 12h, obtains oxygen by 150 DEG C of processing 7h
Change iron, number CL10.
Sample physico-chemical property obtained by 1 embodiment of table and comparative example
Macropore concentration degree is the positive and negative 20%(0.8D-1.2D of macropore most probable pore size) between in macropore account for the ratio of entire macropore
Example.By embodiment and comparative example result, it can be concluded that, the method for the present invention can prepare the macroporous iron oxide of high quality, without
Using operating procedure of the invention, the iron oxide prepared in the case where same material proportion is non-porous common iron oxide, no
Contain macroporous structure.
Claims (19)
1. a kind of macroporous iron oxide, the macroporous iron oxide has the feature that constituent is alpha-ferric oxide, has two-stage hole
Road, intermediary hole most probable pore size is having a size of 15~25nm；The pore diameter range of macropore is 50~1500nm, macropore most probable pore size
D is 60-1000nm, wherein the ratio that the macropore between 0.8D-1.2D accounts for entire macropore is greater than 60%.
2. according to claim 1 macroporous iron oxide, wherein the macroporous iron oxide specific surface area be 50~150 m2/g。
3. a kind of synthetic method of macroporous iron oxide, the method includes following contents:
(1) Beta molecular sieve is mixed with PhCOONa solution, is separated by solid-liquid separation after mixing, and to the solid being collected into
It is dried；
(2) the Beta molecular sieve for obtaining step (1), ferric nitrate, glucide and water are uniformly mixed；
(3) by the obtained dry materials of step (2) to moisture evaporating completely；
(4) solid material for obtaining step (3) is handled in nitrogen or inert atmosphere high temperature；
(5) solid material for obtaining step (4) is in the processing of air atmosphere high temperature；
(6) solid material that step (5) obtains is mixed with lye, in 100~200 DEG C of 1~10h of processing, then crosses washing, does
It is dry to obtain macroporous iron oxide.
4. synthetic method described in accordance with the claim 3, wherein include a pre-treatment step (1A) before step (1), first
The Beta molecular sieve is put into screening solution, allows Beta molecular sieve natural subsidence in screening solution, when molecular sieve is heavy
When dropping to screening liquid bottom, screening liquid is divided into the sectionals such as n, n value is the odd number greater than 1, when screening molecular sieve, according to
The molecular sieve for needing to select different sections preferably selects the molecular sieve of bosom section, and the molecular sieve filtration filtered out is done
It is dry.
5. synthetic method according to claim 4, wherein the screening solution is aqueous solution of propylene glycol, glycerine is water-soluble
The concentration of any one of liquid, the screening solution is 5~75wt%, preferably 10~70wt%；Screen solution and Beta molecule
The mass ratio of sieve is 1~10:1, preferably 2~8:1.
6. synthetic method described in accordance with the claim 3, wherein sodium benzoate mass concentration is 2~20wt% in step (1), excellent
Select 3~18wt%；It is 1~10:1, preferably 2~8:1 that PhCOONa solution and solid matter liquid, which consolidate mass ratio,.
7. synthetic method described in accordance with the claim 3, wherein drying condition described in step (2) is 100~150 DEG C of items
5~15h is handled under part, handles 6~12h under the conditions of preferably 110~140 DEG C.
8. synthetic method described in accordance with the claim 3, wherein Beta molecular sieve, ferric nitrate, carbohydrate described in step (2)
Substance, water mass ratio be 0.1~2:1:0.1~2:10~33, preferably 0.2~1:1:0.2~1:12~30.
9. synthetic method described in accordance with the claim 3, wherein glucide described in step (2) includes sucrose, glucose
One or more of.
10. synthetic method described in accordance with the claim 3, wherein drying temperature described in step (3) is 100~150 DEG C.
11. synthetic method described in accordance with the claim 3, wherein high-temperature process temperature described in step (4) is 300~900
DEG C, preferably 400~800 DEG C；Calcining time is 1~10h, preferably 2~8h.
12. synthetic method described in accordance with the claim 3, wherein high-temperature process temperature described in step (5) is 300~900
DEG C, preferably 400~800 DEG C；Calcining time is 1~10h, preferably 2~8h.
13. synthetic method described in accordance with the claim 3, wherein step (6) lye is sodium hydroxide, potassium hydroxide, hydroxide
One or more of solution such as lithium, concentration of lye are 15~55wt%, preferably 20~50wt%；The lye and solid material
Mass ratio is 1~10:1, preferably 2~8:1.
14. synthetic method described in accordance with the claim 3, wherein treatment temperature is 100~200 DEG C in step (6), preferably
120~180 DEG C；The processing time is 1~10h, preferably 2~8h.
15. synthetic method described in accordance with the claim 3, wherein washing described in step (6) is to be washed with distilled water；Step
(6) drying condition described in is that 5~15h is handled under the conditions of 100~150 DEG C, processing 6 under the conditions of preferably 110~140 DEG C~
12h。
16. synthetic method described in accordance with the claim 3, wherein the Beta molecular sieve is prepared via a method which: by alkali
Source, silicon source, silicon source, water and template (TEAOH) are according to 3~8Na of molar ratio2O:40~100SiO2: A12O3: 800~
1200H2The ratio of O:10~30TEAOH is uniformly mixed, be then charged into closed reactor at 100~180 DEG C crystallization 10~
60h is finally separated, washed, dried, and obtains Beta molecular sieve.
17. synthetic method according to claim 16, wherein the inorganic base is sodium hydroxide；Silicon source be sodium aluminate,
One or more of aluminum sulfate, aluminium chloride, aluminum nitrate；Silicon source is White Carbon black and/or silica solution；Template is tetraethyl hydrogen-oxygen
Change ammonium.
18. synthetic method according to claim 16, wherein the crystallization temperature is 100~180 DEG C, when reaction
Between be 10~60h, preferable reaction temperature be 105~160 DEG C, the reaction time be 20~50h.
19. synthetic method according to claim 16, wherein wash to be washed with distilled water；The drying condition is
5~15h is handled under the conditions of 100~150 DEG C, handles 6~12h under the conditions of preferably 110~140 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101723469A (en) * | 2009-12-18 | 2010-06-09 | 北京工业大学 | Soft and hard double template method for preparing three-dimensional ordered macroporous iron oxide with mesoporous pore wall |
| CN102730770A (en) * | 2012-06-05 | 2012-10-17 | 浙江师范大学 | Preparation method of spongy porous composite oxide nanoscale or microscale polyhedrons |
| CN104229818A (en) * | 2013-06-18 | 2014-12-24 | 中国石油天然气股份有限公司 | Synthetic method of beta molecular sieve |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723469A (en) * | 2009-12-18 | 2010-06-09 | 北京工业大学 | Soft and hard double template method for preparing three-dimensional ordered macroporous iron oxide with mesoporous pore wall |
| CN102730770A (en) * | 2012-06-05 | 2012-10-17 | 浙江师范大学 | Preparation method of spongy porous composite oxide nanoscale or microscale polyhedrons |
| CN104229818A (en) * | 2013-06-18 | 2014-12-24 | 中国石油天然气股份有限公司 | Synthetic method of beta molecular sieve |
Non-Patent Citations (2)
| Title |
|---|
| 夏维涛等: ""介孔氧化铁的合成及表征"", 《第十七届全国分子筛学术大会》 * |
| 王斌等: ""盐溶液改性南阳麦饭石的研究"", 《化工矿物与加工》 * |
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