CN1470323A - Magnetic nano solid base catalyst and its preparnig method - Google Patents
Magnetic nano solid base catalyst and its preparnig method Download PDFInfo
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- CN1470323A CN1470323A CNA02125589XA CN02125589A CN1470323A CN 1470323 A CN1470323 A CN 1470323A CN A02125589X A CNA02125589X A CN A02125589XA CN 02125589 A CN02125589 A CN 02125589A CN 1470323 A CN1470323 A CN 1470323A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 239000007787 solid Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title description 6
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 53
- 238000002360 preparation method Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002585 base Substances 0.000 claims description 19
- 239000012266 salt solution Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229960001545 hydrotalcite Drugs 0.000 claims description 7
- 238000009938 salting Methods 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000454 talc Substances 0.000 abstract description 3
- 229910052623 talc Inorganic materials 0.000 abstract description 3
- 235000012222 talc Nutrition 0.000 abstract description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 abstract 1
- 230000005389 magnetism Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000006911 nucleation Effects 0.000 abstract 1
- 238000010899 nucleation Methods 0.000 abstract 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 238000000643 oven drying Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 229910020068 MgAl Inorganic materials 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 235000015110 jellies Nutrition 0.000 description 3
- 239000008274 jelly Substances 0.000 description 3
- 239000011858 nanopowder Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910001051 Magnalium Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
-
- B01J35/23—
-
- B01J35/33—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
Abstract
The invention provides a kind of magnetic nano solid alkali catalyst and the manufacturing method. The catalyst is covered with solid alkali active element around magnetic nucleus, uses liquid-liquid reaction reversal film reactor to carries on quick nucleation reaction to produce the magnetic nucleus. Blends the nucleus with the salt liquid, and uses the reactor to carries on nuclear reaction, and gets the water talcum which contains magnetic nucleus, bakes the talcum with high temperature into solid alkali oxide, the magnetic is in the compound. The character of the catalyst is: it has nano grade particle size, and high activity and slectivity; it can realize the reclaim of the catalyst by adding on magnetism field.
Description
Technical field: the present invention relates to a kind of magnetic Nano solid base catalyst and preparation method thereof.
Technical background: in the catalyticing research field, homogeneous catalysis is used solid base to replace liquid base to carry out catalysis and is had following advantage: (1) high activity, high selectivity, product purity height progressively to the heterogeneous catalysis transition; (2) catalyst is easy to separate; (3) corrosivity to equipment is little, and the waste liquid of generation is few, reduces environmental pollution.But often there are drawbacks such as reaction interface is little, resistance to mass tranfer is big in heterogeneous catalytic system, make catalytic performance have significantly and reduce than homogeneous system, or owing to some other reason can't extensive use.
Hydrotalcite (LDH) compounds shows good prospects for application in the heterogeneous catalysis research field, can effectively bring into play the shape effect of selecting by controlling precursor crystallite dimension and distribution thereof and modulation pore structure; Extremely tiny through the nanoscale composite metal oxide particle size that the precursor calcining forms, specific area is very big, can fully contact with matrix, realizes catalytic activity efficiently, and has good heat endurance.Shortcoming is in liquid-solid catalyst system and catalyzing bad dispersibility, is difficult to separate and reclaim; Tiny at gas-solid catalysis System Catalyst particle, cause bed resistance big, for its commercial Application has been brought difficulty.
EP0421677Al, EP0421678Al have described the solid base catalyst of the hydrotalcite of alkaline water talcum and process roasting as synthetic alcohol ether, and the general formula of hydrotalcite is [M
2+ aN
3+ b(OH)
(2a+3b)] [X]
b, wherein M is a bivalent metal ion, and N is a trivalent metal ion, and X is an anion of equal value, then becomes the Mg-Al-O compound through roasting.But all do not speak of the dispersion that how to solve catalyst, separate problem such as recovery.
Summary of the invention: the invention provides a kind of nanoscale solids base catalyst that has magnetic, be a kind of catalyst that coats the solid base active component outside magnetic core, it in use can be by the high degree of dispersion of catalyst granules and the enriching and recovering of post catalyst reaction in control magnetic field intensity of externally-applied magnetic field and the direction realization response system.This Preparation of catalysts method is, adopting being all-trans of liquid-liquid reactions to mix liquid film reactor earlier becomes the method for nuclear reaction (to see patent application: 00132145.5) prepare nano-scale magnetic nuclear fast, with this magnetic core and corresponding salt solution mix, utilize the mixed liquid film reactor that is all-trans to become nuclear reaction fast again, obtain containing the hydrotalcite of magnetic core, change corresponding solid base composite oxides into through the high-temperature roasting hydrotalcite, magnetic core is covered by in the composite oxides.
The chemical formula of the magnetic Nano solid base catalyst that the present invention is prepared is:
M-N-(O)/M’Fe
2O
4
Its content is:
M’Fe
2O
4：15％～38％；
M-N-(O)：85％～62％。Wherein M is bivalent metal ion Mg
2+, Ni
2+, Zn
2+, Ca
2+Or Co
2+Wherein any, N is trivalent metal ion Fe
3+, V
3+, Al
3+Or Gr
3+Wherein any; M ' is Mg
2+, Cu
2+, Ba
2+, Ni
2+Wherein any of trivalent metal ion, M and M ' can be the same or different;
M ' Fe
2O
4Be magnetic species, M-N-(O) is for being coated on M ' Fe
2O
4The outer composite oxides that form through roasting by corresponding hydrotalcite.
This Preparation of catalysts method is:
(1). nano-magnetic nuclear M ' Fe
2O
4The powder preparation
Soluble inorganic salt and the ferric soluble inorganic salt of M ' are mixed with mixed solution, wherein M '/Fe
3+Mol ratio is 0.5～2.0, and the molar concentration of M ' is 0.1～2.5M, Fe
3+Molar concentration be 0.2～5.0M; With NaOH and Na
2CO
3The preparation mixed ammonium/alkali solutions, wherein the NaOH molar concentration is 0.1～5.0M, Na
2CO
3Molar concentration is 0.1～4.8M;
Pour above-mentioned salting liquid and aqueous slkali into the mixed liquid film reactor that is all-trans (seeing patent application 00132145) simultaneously, the rotating speed of control rotor is 1000～8000rpm, material time of staying in reactor is 1-8min, after liquid branch device disperses, fully mix with the place, slit between the stator at rotor, be discharged to crystallizing kettle through discharging opening, at 80～120 ℃ of thermostatic crystallization 2～10h, suction filtration, washing repeatedly, drying obtains particle size range at the M ' of 20～80nm Fe through 800～1000 ℃ of high-temperature roastings
2O
4Powder.The addition of aqueous slkali should make the pH value of mixed liquid 8.5～11.0.
(2), magnetic precursor M-N-LDH/M ' Fe
2O
4Preparation
With solubility divalence inorganic metal salt M
2+(X
N-)
2/nWith solubility trivalent inorganic metal salt N
3+(X
N-)
3/nBe mixed with mixing salt solution, M
2+/ N
3+Mol ratio be 2～4, the molar concentration of bivalent metal ion is 0.2～2.5M, the molar concentration of trivalent metal ion is 1.6～4.5M; Press M ' Fe
2O
4With the mass ratio of divalence inorganic metal salt in the above-mentioned mixing salt solution be 1: 17.1～5.0 ratio, take by weighing corresponding M ' Fe
2O
4Powder adds in the mixing salt solution, stirs evenly mixed;
With NaOH and Na
2CO
3The preparation mixed ammonium/alkali solutions.The NaOH molar concentration is 0.1～5.0M, Na
2CO
3Molar concentration is 0.1～4.8M;
Pour salting liquid and aqueous slkali into the mixed liquid film reactor that is all-trans simultaneously, the rotating speed of control rotor is 1000～8000rpm, material time of staying in reactor is 1-8min, after liquid branch device disperses, fully mix with the place, slit between the stator at rotor, be discharged to crystallizing kettle through discharging opening, at 80～120 ℃ of thermostatic crystallization 4～10h, suction filtration, washing repeatedly, drying obtain carrying magnetic nuclear M ' Fe
2O
4Hydrotalcite M-N-LDH/M ' Fe
2O
4The addition of aqueous slkali should make the pH value of mixed liquid 8.5～11.0
(3), catalyst M-N-(O)/M ' Fe
2O
4Preparation
With above-mentioned M-N-LDH/M ' Fe
2O
4Roasting is 2～5 hours in 400～600 ℃, and 10 ℃/minute of heating rates obtain particle size range at the magnetic solid base catalyst M-N-of 30～100nm (O)/M ' Fe
2O
4
The trivalent salt of iron can be in the step (1): Fe
2(SO
4)
3, Fe Cl
3Or Fe (NO
3)
3In any; M ' salt can be: M ' SO
4, M ' Cl
2, M ' (NO
3)
2In any, the preferred Zn of M '
2+, Mg
2+Or Ni
2+
X is Cl in the step (2)
-, SO
4 2-, NO
3 -, CO
3 2-In any, n is the valence state of anion X, n=1 or 2.
Because the preparation magnetic core all adopts the mixed liquid film reactor that is all-trans to become nuclear reaction fast with solid base catalyst, can make the instantaneous abundant contact of reactant, collision, become that nuclear reaction is instantaneous to be finished, the nucleus simultaneous growth is so magnetic core that obtains and solid base catalyst are the particle of nano-scale.At synthetic M-N-LDH/M ' Fe
2O
4In the process, because a large amount of nucleus is examined M ' Fe at magnetic
2O
4Surface synchronous growth under identical crystallization condition has guaranteed the uniformity of clad structure.This catalyst particle size is at 30～100nm, and its magnetic property index: coercivity H is 120～108A/m, specific saturation magnetization σ
xBe 2～18A/m.Because this catalyst has magnetic, in use can be by the high degree of dispersion of catalyst granules and the enriching and recovering of post catalyst reaction in control magnetic field intensity of externally-applied magnetic field and the direction realization response system, thus such catalyst is difficult to the difficult problem disperseing, reclaim before having solved.
The specific embodiment:
[embodiment 1]
(1) magnetic core MgFe
2O
4The preparation of nano-powder
With magnesium/iron mol ratio is 1: 2 ratio, takes by weighing 8.46gMg (NO
3)
26H
2O and 27.07gFe (NO
3)
39H
2O is dissolved in the 130ml ionized water and is made into mixing salt solution, takes by weighing 6.40gNaOH and 14.20gNa
2CO
3Be dissolved in the 130ml deionized water and be made into mixed ammonium/alkali solutions; Salting liquid and aqueous slkali are poured in the mixed liquid film reactor of having opened that is all-trans simultaneously, the rotating speed of rotor is controlled at 3000rpm, reaction mixture stops 5min in reactor, pour the slurries that obtain into crystallizing kettle again, in 100 ℃ of following thermostatic crystallization 6h, then repeatedly suction filtration, wash to the pH value and equal 7, filter cake is placed porphyrize behind 70 ℃ of oven drying 24h, roasting 2h in 900 ℃, air atmosphere again, 10 ℃/minute of heating rates make magnetic nuclear MgFe
2O
4
(2) magnetic precursor MgAl-LDH/MgFe
2O
4Preparation
With the magnalium mol ratio is 3: 1 ratio, takes by weighing 38.46gMg (NO
3)
26H
2O and 18.78gAl (NO
3)
39H
2O is dissolved in the 130ml deionized water and is made into mixing salt solution, and with Mg (NO
3)
26H
2O/MgFe
2O
4Mol ratio is 17.10 ratio, with the MgFe that makes
2O
4Powder adds in the mixing salt solution, stirs evenly mixed; Take by weighing 12.8gNaOH and 10.6gNa
2CO
3Be dissolved in the 130ml deionized water and be made into mixed ammonium/alkali solutions; Pouring above-mentioned two kinds of solution into opened be all-trans simultaneously mixes in the liquid film reactor, the rotating speed of rotor is controlled at 3000rpm, reaction mixture stops 5.0min in reactor, pour the jelly that obtains into crystallizing kettle again, in 100 ℃ of following thermostatic crystallization 6h, then repeatedly suction filtration, wash to the pH value and equal 7, place oven drying 24h promptly to get magnetic precursor MgAl-LDH/MgFe filter cake
2O
4
(3) catalyst MgAl (O)/MgFe
2O
4Preparation
With magnetic precursor MgAl-LDH/MgFe
2O
4Roasting is 2 hours in 600 ℃ of air atmosphere, and 10 ℃/minute of heating rates obtain magnetic solid base catalyst MgAl (O)/MgFe
2O
4
Record this catalyst crystallite dimension in 30～85nm scope, the most probable crystallite dimension is 62nm.The coercivity H value is 120.0A/m, specific saturation magnetization 6
xBe 2.1A/m.
[embodiment 2]
(1) magnetic core NiFe
2O
4The preparation of nano-powder
With nickel/iron mol ratio is 1: 2 ratio, takes by weighing 9.60g Ni (NO
3)
26H
2O and 27.07g Fe (NO
3)
39H
2O is dissolved in the 130ml ionized water and is made into mixing salt solution, takes by weighing 8.00gNaOH and 14.20gNa
2CO
3Be dissolved in the 130ml deionized water and be made into mixed ammonium/alkali solutions; Salting liquid and aqueous slkali are poured in the mixed liquid film reactor of having opened that is all-trans simultaneously, the rotating speed of rotor is controlled at 5000rpm, reaction mixture stops 3min in reactor, pour the slurries that obtain into crystallizing kettle again, in 100 ℃ of following thermostatic crystallization 6h, then repeatedly suction filtration, wash to the pH value and equal 7, filter cake is placed porphyrize behind 70 ℃ of oven drying 24h, roasting 2h in 900 ℃, air atmosphere again, 10 ℃/minute of heating rates make magnetic nuclear NiFe
2O
4
(2) magnetic precursor ZnAl-LDH/NiFe
2O
4Preparation
With zinc/al mole ratio is 2: 1 ratio, takes by weighing 39.56gZn (NO
3)
26H
2O and 25.13gAl (NO
3)
3.9H
2O is dissolved in the 130ml deionized water and is made into mixing salt solution, and with Zn (NO
3)
26H
2O/NiFe
2O
4Mol ratio is 11.40 ratio, with the NiFe that makes
2O
4Powder adds in the mixing salt solution, stirs evenly mixed; Take by weighing 14.4gNaOH and 10.6gNa
2CO
3Be dissolved in the 130ml deionized water and be made into mixed ammonium/alkali solutions; Pouring above-mentioned two kinds of solution into opened be all-trans simultaneously mixes in the liquid film reactor, the rotating speed of rotor is controlled at 5000rpm, reaction mixture stops 3min in reactor, pour the jelly that obtains into crystallizing kettle again, in 100 ℃ of following thermostatic crystallization 6h, then repeatedly suction filtration, wash to the pH value and equal 7, place oven drying 24h promptly to get magnetic precursor ZnAl-LDH/NiFe filter cake
2O
4
(3) catalyst ZnAl (O)/NiFe
2O
4Preparation
With magnetic precursor ZnAl-LDH/NiFe
2O
4Roasting is 5 hours in 600 ℃ of air atmosphere, and 10 ℃/minute of heating rates obtain magnetic solid base catalyst ZnAl (O)/NiFe
2O
4
Record crystallite dimension in 30～80nm scope, the most probable crystallite dimension is 58nm.The coercivity H value is 110.5A/m, specific saturation magnetization 6
xBe 3: 5A/m
[embodiment 3]
(1) magnetic core NiFe
2O
4The preparation of nano-powder
With nickel/iron mol ratio is 1: 2 ratio, takes by weighing 9.60gZn (NO
3)
26H
2O and 27.07gFe (NO
3)
39H
2O is dissolved in the 130ml ionized water and is made into mixing salt solution, takes by weighing 8.80gNaOH and 10.65gNa
2CO
3Be dissolved in the 130ml deionized water and be made into mixed ammonium/alkali solutions; Salting liquid and aqueous slkali are poured in the mixed liquid film reactor of having opened that is all-trans simultaneously, the rotating speed of rotor is controlled at 7000rpm, reaction mixture stops 2min in reactor, pour the slurries that obtain into crystallizing kettle again, in 100 ℃ of following thermostatic crystallization 6h, then repeatedly suction filtration, wash to the pH value and equal 7, filter cake is placed porphyrize behind 70 ℃ of oven drying 24h, roasting 2h in 900 ℃, air atmosphere again, 10 ℃/minute of heating rates make magnetic nuclear NiFe
2O
4
(2) magnetic precursor MgAl-LDH/NiFe
2O
4Preparation
With the magnalium mol ratio is 4: 1 ratio, takes by weighing 41.03gMg (NO
3)
26H
2O and 15.01gAl (NO
3)
39H
2O is dissolved in the 130ml deionized water and is made into mixing salt solution, and with Mg (NO
3)
26H
2O/NiFe
2O
4Mol ratio is 5.00 ratio, with the NiFe that makes
2O
4Powder adds in the mixing salt solution, stirs evenly mixed; Take by weighing 12.8gNaOH and 8.48gNa
2CO
3Be dissolved in the 130ml deionized water and be made into mixed ammonium/alkali solutions; Pouring above-mentioned two kinds of solution into opened be all-trans simultaneously mixes in the liquid film reactor, the rotating speed of rotor is controlled at 7000rpm, reaction mixture stops 2min in reactor, pour the jelly that obtains into crystallizing kettle again, in 100 ℃ of following thermostatic crystallization 6h, then repeatedly suction filtration, wash to the pH value and equal 7, place oven drying 24h promptly to get magnetic precursor MgAl-LDH/NiFe filter cake
2O
4
(3) catalyst MgAl (O)/NiFe
2O
4Preparation
With magnetic precursor MgAl-LDH/NiFe
2O
4Roasting is 2 hours in 550 ℃ of air atmosphere, and 10 ℃/minute of heating rates obtain magnetic solid base catalyst MgAl (O)/NiFe
2O
4
Record crystallite dimension in 35～90nm scope.The most probable crystallite dimension is 65nm.The coercivity H value is 130.2A/m, specific saturation magnetization 6
xBe 2.6A/m.
Claims (3)
1 one kinds of magnetic Nano solid base catalysts, its chemical formula is:
M-N-(O)/M’Fe
2O
4
Its content is:
M’Fe
2O
4：15％～38％；
M-N-(O): 85%～62%; Wherein M is bivalent metal ion Mg
2+, Ni
2+, Zn
2+, Ca
2+Or Co
2+Wherein any, N is trivalent metal ion Fe
3+, V
3+, Al
3+Or Gr
3+Wherein any, M ' is Mg
2+, Cu
2+, Ba
2+, Ni
2+Wherein any of trivalent metal ion, M and M ' can be the same or different;
M ' Fe
2O
4Be magnetic species, M-N-(O) is for being coated on M ' Fe
2O
4The outer composite oxides that form through roasting by corresponding hydrotalcite.
2. the preparation method of a magnetic Nano solid base catalyst as claimed in claim 1, step is as follows:
(1). nano-magnetic nuclear M ' Fe
2O
4The powder preparation
Soluble inorganic salt and the ferric soluble inorganic salt of M ' are mixed with mixed solution, wherein M '/Fe
3+Mol ratio is 0.5～2.0, and the molar concentration of M ' is 0.1～2.5M, Fe
3+Molar concentration be 0.2～5.0M; With NaOH and NaCO
3The system mixed ammonium/alkali solutions, wherein the NaOH molar concentration is 0.1～5.0M, Na
2CO
3Molar concentration is 0.1～4.8M;
Pour above-mentioned salting liquid and aqueous slkali into the mixed liquid film reactor that is all-trans simultaneously, the rotating speed of control rotor is 1000～8000rpm, material time of staying in reactor is 1～8min, after liquid branch device disperses, fully mix with the place, slit between the stator at rotor, be discharged to crystallizing kettle through discharging opening, at 80～120 ℃ of thermostatic crystallization 2～10h, suction filtration, washing repeatedly, drying obtains particle size range at the M ' of 0～80nm Fe through 800～1000 ℃ of high-temperature roastings
2O
4Powder; The amount of aqueous slkali should make the pH value of mixed liquid 8.5～11.0;
(2), magnetic precursor M-N-LDH/M ' Fe
2O
4Preparation
With solubility divalence inorganic metal salt M
2+(X
N-)
2/nWith solubility trivalent inorganic metal salt N
3+(X
N-)
3/nBe mixed with mixing salt solution, M
2+/ N
3+Mol ratio be 2～4, the molar concentration of bivalent metal ion is 0.2～2.5M, the molar concentration of trivalent metal ion is 1.6～4.5M; Press M ' Fe
2O
4With the mass ratio of divalence inorganic metal salt in the above-mentioned mixing salt solution be 1: 17～5 ratio, take by weighing corresponding M ' Fe
2O
4Powder adds in the mixing salt solution, stirs evenly mixed; With NaOH and Na
2CO
3The preparation mixed ammonium/alkali solutions, the NaOH molar concentration is 0.1～5.0M, Na
2CO
3Molar concentration is 0.1～4.8M;
Pour salting liquid and aqueous slkali into the mixed liquid film reactor that is all-trans simultaneously, the rotating speed of control rotor is 1000～8000rpm, material time of staying in reactor is 1-8min, after liquid branch device disperses, fully mix with the place, slit between the stator at rotor, be discharged to crystallizing kettle through discharging opening, at 80～120 ℃ of thermostatic crystallization 4～10h, suction filtration, washing repeatedly, drying obtain carrying magnetic nuclear M ' Fe
2O
4Hydrotalcite M-N-LDH/M ' Fe
2O
4The amount of aqueous slkali should make the pH value of mixed liquid 8.5～11.0;
(3), catalyst M-N-(O)/M ' Fe
2O
4Preparation
With above-mentioned M-N-LDH/M ' Fe
2O
4Roasting is 2～5 hours in 400～600 ℃, and 10 ℃/minute of heating rates obtain particle size range at the magnetic solid base catalyst M-N-of 20～100nm (O)/M ' Fe
2O
4
3. the preparation method of magnetic Nano solid base catalyst according to claim 1 is characterized in that:
The trivalent salt of iron can be in the step (1): Fe
2(SO
4)
3, FeCl
3Or Fe (NO
3)
3In any; M ' salt can be: M ' SO
4, M ' Cl
2, M ' (NO
3)
2In any, the preferred Mg of M '
2+Or Ni
2+
X is Cl in the step (2)
-, SO
4 2-, NO
3 -, CO
3 2-In any, n is the valence state of anion X, n=1 or 2.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02125589XA CN1180881C (en) | 2002-07-23 | 2002-07-23 | Magnetic nano solid base catalyst and its preparnig method |
| AU2003255081A AU2003255081A1 (en) | 2002-07-23 | 2003-07-23 | Magnetic nanometer solid base catalyst and its preparation method |
| PCT/CN2003/000592 WO2004009233A1 (en) | 2002-07-23 | 2003-07-23 | Magnetic nanometer solid base catalyst and its preparation method |
| US11/040,408 US7247598B2 (en) | 2002-07-23 | 2005-01-21 | Nano-scale magnetic solid base catalyst and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02125589XA CN1180881C (en) | 2002-07-23 | 2002-07-23 | Magnetic nano solid base catalyst and its preparnig method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1470323A true CN1470323A (en) | 2004-01-28 |
| CN1180881C CN1180881C (en) | 2004-12-22 |
Family
ID=30121261
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB02125589XA Expired - Fee Related CN1180881C (en) | 2002-07-23 | 2002-07-23 | Magnetic nano solid base catalyst and its preparnig method |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1180881C (en) |
| AU (1) | AU2003255081A1 (en) |
| WO (1) | WO2004009233A1 (en) |
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- 2002-07-23 CN CNB02125589XA patent/CN1180881C/en not_active Expired - Fee Related
-
2003
- 2003-07-23 WO PCT/CN2003/000592 patent/WO2004009233A1/en not_active Application Discontinuation
- 2003-07-23 AU AU2003255081A patent/AU2003255081A1/en not_active Abandoned
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Also Published As
| Publication number | Publication date |
|---|---|
| AU2003255081A1 (en) | 2004-02-09 |
| CN1180881C (en) | 2004-12-22 |
| WO2004009233A1 (en) | 2004-01-29 |
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