CN109502603A - A kind of magnetic molecule preparation method sieved and obtained magnetic molecule sieve - Google Patents
A kind of magnetic molecule preparation method sieved and obtained magnetic molecule sieve Download PDFInfo
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- CN109502603A CN109502603A CN201710828026.9A CN201710828026A CN109502603A CN 109502603 A CN109502603 A CN 109502603A CN 201710828026 A CN201710828026 A CN 201710828026A CN 109502603 A CN109502603 A CN 109502603A
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- molecular sieve
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- 230000005291 magnetic effect Effects 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002808 molecular sieve Substances 0.000 claims abstract description 172
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 170
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 36
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 28
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005342 ion exchange Methods 0.000 claims abstract description 24
- 229910052665 sodalite Inorganic materials 0.000 claims abstract description 17
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 6
- 238000012805 post-processing Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 152
- 239000012298 atmosphere Substances 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 35
- 239000001257 hydrogen Substances 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- 229910052742 iron Inorganic materials 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000009938 salting Methods 0.000 claims description 17
- 230000005415 magnetization Effects 0.000 claims description 16
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical group N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 14
- 239000005695 Ammonium acetate Substances 0.000 claims description 14
- 229940043376 ammonium acetate Drugs 0.000 claims description 14
- 235000019257 ammonium acetate Nutrition 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 229910052596 spinel Inorganic materials 0.000 claims description 5
- 239000011029 spinel Substances 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 230000005012 migration Effects 0.000 description 7
- 238000013508 migration Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 230000005389 magnetism Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001959 radiotherapy Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of magnetic molecule sieve and obtained magnetic molecule sieves, wherein the method is as follows: ammonium salt and molysite is respectively adopted and successively carries out ion exchange with NaY type molecular sieve, then carries out the post-processing such as three sections of roastings, obtains Fe3O4- Fe/Y type molecular sieve, i.e., the described magnetic molecule sieve.In magnetic molecule sieve, Fe3O4The magnetic molecule sifter device that particle and Fe particle are located in the sodalite cage of molecular sieve, and obtain has very high Curie temperature and good magnetic behavior.The method of the invention is simple, it is easy to accomplish, operating condition is mild, and it is environmentally protective, and it is suitble to industrialized production and application；Magnetic molecule sieve structure of the present invention is stablized, and not easily runs off Fe in use3O4And/or Fe, thus long service life, effect are good, and magnetic molecule sieve can recycle.
Description
Technical field
The present invention relates to molecular sieve arts more particularly to magnetic molecule to sieve, and particularly, is related to a kind of system of magnetic molecule sieve
Preparation Method and obtained magnetic molecule sieve.
Background technique
Molecular sieve has uniform microcellular structure, good absorption, ion-exchange catalyst performance, so that molecular sieve is being permitted
It is multi-field to be widely used.But simple zeolite molecular sieve, since density is smaller, powder is meticulous, is often nanometer
Or micron powder, it is necessary to could have excellent using effect after being modified.
The unique structure and properties of molecular sieve, keep molecular sieve very widely used.It is used as catalyst still but regardless of it
Adsorbent requires to be rapidly performed by separation of solid and liquid in being catalyzed and adsorbing each operating unit, but utilizes traditional separation skill
Art carries out separation molecular sieve rapidly and efficiently and mother liquor is relatively difficult.
And since early 20th century, magnetic carrier technology (MCT) just appears in Industrial Catalysis in a variety of forms, this skill
Art is cheap and efficient.Currently, MCT technology have been widely used for biological medicine, radiotherapy, wastewater treatment, Industrial Catalysis and
During mineral processing etc. is complicated, and huge application prospect is shown in these fields.
The essence of magnetic carrier technology is that will have ferromagnetic substance to evenly spread to weak by different preparation processes
Inside the magnetic or non-magnetic substance with specific function or surface, enables substance to reach under the action of external magnetic field with system
To the purpose of separation.MCT is to be proposed by Uthain when studying wastewater treatment the 1940s first, it overcomes many
The limitation of conventional separation techniques.
And MCT technological transformation molecular sieve is utilized, the magnetism of molecular sieve is not only increased, and also increase the steady of molecular sieve
It is qualitative.
Synthesizing magnetic molecular sieve is mainly the following synthesis thinking at present:
(1) molecular sieve surface is modified using magnetic metal nano particle.The method passes through infusion process for metal ion
Molecular sieve surface is introduced, is then reduced to simple substance with reducing agents such as hydrogen or sodium borohydrides.Although this method is easy to be fast
Victory, but magnetic-particle is easy to fall off on surface, so that material is easy to lose magnetism；
(2) molecular sieve surface is modified using magnetic metal oxide.The method is that molecular sieve is dispersed in magnetic gold
Belong in solion, adds precipitating reagent or roasting direct in molecular sieve surface and form magnetic metal oxide.This same appearance
Easily cause falling off for magnetic-particle；
(3) molecular sieve and magnetisable material are binded using gluing method.Although this way magnetic saturation intensity is higher,
That stability is poor, therewith binder failure and fail；
(4) magnetic material is introduced in the synthetic system of molecular sieve, thus synthesizing magnetic molecular sieve.This method has energy
It consumes low, the advantages that strong operability, but tends to impact the structure and adsorption capacity of molecular sieve, the later period is applied
It is unfavorable.
Summary of the invention
In order to overcome the above problem, present inventor has performed sharp studies, first using ion exchange twice, then pass through three
Section roasting obtains the magnetic molecule sieve, thereby completing the present invention.
One of the objects of the present invention is to provide a kind of preparation methods of magnetic molecule sieve, are embodied in following side
Face:
(1) a kind of preparation method of magnetic molecule sieve, which is characterized in that the described method comprises the following steps:
Step 1 is modified molecular sieve, obtains HY type molecular sieve；
Step 2, the HY type molecular sieve that step 1 is obtained and soluble iron salting liquid carry out ion exchange；
Step 3 is post-processed, and the magnetic molecule sieve is obtained.
(2) method according to above-mentioned (1), which is characterized in that carry out step 1 before step 1 ':
Step 1 ', molecular sieve is activated；
Preferably, the activation processing carries out at 400~600 DEG C, it is highly preferred that the activation processing is in 450-550
It carries out at DEG C, such as is carried out at 500 DEG C；
And/or
Step 1 includes following sub-step:
Step 1-1, molecular sieve is added in ammonium salt solution and is modified；
Step 1-2, it filtered, dried and is roasted after being modified, obtain HY type molecular sieve.
(3) method according to above-mentioned (1) or (2), which is characterized in that in step 1-1,
The ammonium salt is selected from ammonium acetate and/or halogeno-amine, it is preferable that the ammonium salt is selected from ammonium acetate and/or ammonium chloride, more
Preferably, the ammonium salt is selected from ammonium acetate；And/or
The concentration of the ammonium salt solution is 0.1~0.5mol/L, preferably 0.1~0.3mol/L, more preferably 0.2mol/
L；And/or
The ratio between weight of molecular sieve and the volume of ammonium salt solution are 1:(20~80), preferably 1:(40~60), more preferably
For 1:(45~55), such as 1:50；And/or
The modification carries out as follows: in 60~120 DEG C carry out 12~for 24 hours, be preferable over 80~100 DEG C carry out 18~for 24 hours, more
Be preferable over 90 DEG C carry out 22~for 24 hours.
(4) method according to one of above-mentioned (1) to (3), which is characterized in that in step 1-2,
The drying carries out at 80~140 DEG C, is preferable at 100~120 DEG C and carries out；And/or
The roasting carries out at 200~800 DEG C, is preferable at 300~700 DEG C and carries out, more preferably in 400~600 DEG C
Lower progress.
(5) method according to one of above-mentioned (1) to (4), which is characterized in that in step 2,
The soluble iron salting liquid includes ferric chloride solution, ferrum sulfuricum oxydatum solutum, iron nitrate solution and acetic acid ferrous solution, excellent
Selection of land, the soluble iron salting liquid includes ferric chloride solution and iron nitrate solution, it is highly preferred that the soluble iron salting liquid
For iron nitrate solution；And/or
The ratio between weight and the volume of soluble iron salting liquid of HY type molecular sieve are 1:(20~80), preferably 1:(40~
60), more preferably 1:(45~55), such as 1:50；And/or
The ion exchange carries out as follows: in 60~120 DEG C of 8~30h of progress, be preferable over 80~100 DEG C carry out 12~
For 24 hours, it is more preferably carried out for 24 hours in 90 DEG C.
(6) method according to one of above-mentioned (1) to (5), which is characterized in that in step 3, the post-processing includes
Separation, dry and roasting；
Preferably, the drying carries out as follows: in air and/or nitrogen, 4~18h is dried at 80~140 DEG C, it is more excellent
It selects in air and/or nitrogen, dry 6~15h at 100~120 DEG C；
(7) method according to above-mentioned (6), which is characterized in that it is described to be roasted to three sections of roastings, wherein the atmosphere roasted
It is followed successively by nitrogen, oxygen and hydrogen；
Preferably: the roasting carries out at 300~700 DEG C, is preferable at 400~600 DEG C and carries out, more preferably in 450-
It is carried out at 550 DEG C；
More preferably: the roasting carries out 4~20h, preferably 8~15h of progress, such as 10h.
(8) method according to above-mentioned (7), which is characterized in that the roasting is successively following to be carried out: under nitrogen atmosphere
2~8h is roasted, 2~8h is roasted under oxygen atmosphere, 1~5h is roasted under atmosphere of hydrogen；Preferably, it is roasted under nitrogen atmosphere
4~6h roasts 4~6h under oxygen atmosphere, and 2~4h is roasted under atmosphere of hydrogen；It is highly preferred that being roasted under nitrogen atmosphere
4h roasts 4h under oxygen atmosphere, roasts 2h under atmosphere of hydrogen.
Second aspect of the present invention provides a kind of magnetic molecule sieve, is embodied in aspect:
(9) a kind of magnetic molecule sieve, it is preferred to use above-mentioned (1) to one of (8) the method is made, which is characterized in that institute
Stating molecular sieve is Fe3O4- Fe/Y type molecular sieve, wherein Fe has been formed in situ in Y molecular sieve3O4Particle and Fe particle；
Preferably, the Fe3O4Particle is spinel structure, and the Fe particle is body-centered cubic structure, and the Fe3O4
Particle and Fe particle are nanoscale；
It is highly preferred that the Fe3O4Particle and Fe particle are located in the sodalite cage of molecular sieve.
(10) magnetic molecule according to above-mentioned (9) sieves, which is characterized in that
The Curie temperature of the magnetic molecule sieve is 500~700 DEG C, preferably 500~600 DEG C, more preferably 550 DEG C；
And/or
Saturation magnetization of the magnetic molecule sieve at 25 DEG C is 8~12emu/g, and the saturated magnetization at 100 DEG C is strong
Degree is 7~10emu/g, it is preferable that saturation magnetization of the magnetic molecule sieve at 25 DEG C is 9~10emu/g, 100 DEG C
Under saturation magnetization be 8~9emu/g.
Detailed description of the invention
Fig. 1 shows the XRD spectra of HY type molecular sieve obtained in embodiment 1 Yu raw material NaY type molecular sieve；
Fig. 2 shows FeY type molecular sieves, Fe obtained in embodiment 12O3/ Y type molecular sieve and Fe3O4- Fe/Y type molecule
The XRD spectra of sieve；
Fig. 3 shows the XRD spectra of FeY type molecular sieve obtained in raw material NaY type molecular sieve and embodiment 1；
Fig. 4 shows the Fe that embodiment 1 obtains3O4The Curie temperature curve graph of-Fe/Y type molecular sieve；
Fig. 5 shows the Fe that embodiment 1 obtains3O4Hysteresis loop of-Fe/Y type the molecular sieve at 25 DEG C；
Fig. 6 shows the Fe that embodiment 1 obtains3O4Hysteresis loop of-Fe/Y type the molecular sieve at 100 DEG C.
Specific embodiment
Below by embodiment and experimental example, the present invention is described in more detail.Illustrated by these, spy of the invention
Point and advantage will become more apparent from clear.
The present invention provides a kind of preparation methods of magnetic molecule sieve, the described method comprises the following steps:
Step 1 is modified molecular sieve, obtains HY type molecular sieve.
A kind of preferred embodiment according to the present invention, in step 1, the molecular sieve are Y-type zeolite molecular sieve.
In further preferred embodiment, in step 1, the molecular sieve is NaY type zeolite molecular sieve.
Wherein, the silica alumina ratio of the NaY type molecular sieve is 5.0~5.3, specific surface area >=720m2/ g, relative crystallinity >=
90%, the size of molecular sieve pore passage is 0.3~1.6um.
A kind of preferred embodiment according to the present invention carries out step 1 before step 1 ':
Step 1 ', molecular sieve is activated.
In further preferred embodiment, in step 1 ' in, the activation processing carries out at 400~600 DEG C.
In embodiment still more preferably, in step 1 ' in, the activation processing carries out at 450-550 DEG C,
Such as it is carried out at 500 DEG C.
Wherein, molecular sieve is activated, in this way, the impurity such as carbon deposit can be removed, it is preferable that activation progress 2~
6h, more preferably 3~5h of progress, such as 4h.
A kind of preferred embodiment according to the present invention, step 1 include following sub-step:
Step 1-1, molecular sieve is added in ammonium salt solution and is modified；
Step 1-2, it filtered, dried and is roasted after being modified, obtain HY type molecular sieve.
A kind of preferred embodiment according to the present invention, in step 1-1, the ammonium salt is selected from ammonium acetate and/or halogenation
Amine.
In further preferred embodiment, in step 1-1, the ammonium salt is selected from ammonium acetate and/or ammonium chloride.
In embodiment still more preferably, in step 1-1, the ammonium salt is selected from ammonium acetate.
Wherein, in step 1-1, by ion exchange by Na in molecular sieve+It is replaced into NH as far as possible4 +。
A kind of preferred embodiment according to the present invention, in step 1-1, the concentration of the ammonium salt solution is 0.1~
0.5mol/L。
In further preferred embodiment, in step 1-1, the concentration of the ammonium salt solution is 0.1~0.3mol/
L。
In embodiment still more preferably, in step 1-1, the concentration of the ammonium salt solution is 0.2mol/L.
A kind of preferred embodiment according to the present invention, in step 1-1, the weight of molecular sieve and the volume of ammonium salt solution
The ratio between be 1:(20~80).
In further preferred embodiment, in step 1-1, the ratio between weight and the volume of ammonium salt solution of molecular sieve
For 1:(40~60).
In embodiment still more preferably, in step 1-1, the volume of the weight of molecular sieve and ammonium salt solution it
Than for 1:(45~55), such as 1:50.
Wherein, in step 1-1, the amount ratio of molecular sieve and ammonium salt solution is the ratio between weight and volume (g/mL).
A kind of preferred embodiment according to the present invention, in step 1-1, the modification carries out as follows: in 60~120 DEG C
Progress 12~for 24 hours.
In further preferred embodiment, in step 1-1, the modification carries out as follows: carrying out in 80~100 DEG C
18~for 24 hours.
In embodiment still more preferably, in step 1-1, the modification carries out as follows: carrying out 22 in 90 DEG C
~for 24 hours.
A kind of preferred embodiment according to the present invention, in step 1-2, the drying carries out at 80~140 DEG C, excellent
It selects and is carried out at 100~120 DEG C.
A kind of preferred embodiment according to the present invention, in step 1-2, the roasting in air and/or nitrogen atmosphere,
It is carried out at 200~800 DEG C.
In further preferred embodiment, in step 1-2, the roasting is in air and/or nitrogen atmosphere, 300
It is carried out at~700 DEG C.
In embodiment still more preferably, in step 1-2, the roasting in air and/or nitrogen atmosphere,
It is carried out at 400~600 DEG C, preferably nitrogen atmosphere.
Wherein, by roasting, NH in molecular sieve after ammonium salt can be promoted to exchange4+Become H+, become HY type molecular sieve, and
And, it is preferable that it more can guarantee the stabilization of HY type molecular sieve in a nitrogen atmosphere.
In the present invention, ammonium salt modification can't damage the crystal structure of molecular sieve, specifically, modified in ammonium salt
Afterwards, (220) in XRD spectra, (311), (331) these three crystal faces the relative intensity of diffraction maximum do not change, only by force
Degree decreases, and illustrates that ammonium salt modification does not damage the crystal structure of NaY type molecular sieve.
Step 2, the HY type molecular sieve that step 1 is obtained and soluble iron salting liquid carry out ion exchange.
Wherein, in step 2, the H in HY type molecular sieve+With the Fe in soluble iron solion3+Ion exchange is carried out,
As much as possible by the H in molecular sieve+It is replaced into Fe3+。
A kind of preferred embodiment according to the present invention, in step 2, the soluble iron salting liquid include that iron chloride is molten
Liquid, ferrum sulfuricum oxydatum solutum, iron nitrate solution and acetic acid ferrous solution.
In further preferred embodiment, in step 2, the soluble iron salting liquid include ferric chloride solution and
Iron nitrate solution.
In embodiment still more preferably, in step 2, the soluble iron salting liquid is iron nitrate solution.
A kind of preferred embodiment according to the present invention, in step 2, the weight and soluble ferric iron salt of HY type molecular sieve are molten
The ratio between volume of liquid is 1:(20~80).
In further preferred embodiment, in step 2, weight and the soluble iron salting liquid of HY type molecular sieve
The ratio between volume is 1:(40~60).
In embodiment still more preferably, in step 2, the weight and soluble iron salting liquid of HY type molecular sieve
The ratio between volume be 1:(45~55), such as 1:50.
A kind of preferred embodiment according to the present invention, in step 2, the ion exchange carry out as follows: in 60~120
DEG C carry out 8~30h.
In further preferred embodiment, in step 2, the ion exchange carries out as follows: in 80~100 DEG C into
Row 12~for 24 hours.
In embodiment still more preferably, in step 2, the ion exchange carries out as follows: carrying out in 90 DEG C
24h。
If directlying adopt NaY type molecular sieve and Fe3+Carry out ion exchange, it is easy to generate Fe (OH)3Precipitating, and it is described
Fe(OH)3Precipitating is difficult to migrate from supercage to sodalite cage, causes to exist only in supercage, even if the later period is formed by roasting
Fe3O4, but the volume of the supercage of molecular sieve is larger, in Fe3O4It is easy to be lost, and leads to the longevity for reducing magnetic molecule sieve
Life.
And in the present invention, first molecular sieve is handled to obtain HY type molecular sieve, then in H+Under the conditions of with Fe3+It carries out
Ion exchange, in this way, can be later period Fe3+Ion exchange process provides acidic environment, and then prevents the Fe (OH) that cannot be migrated3
The generation of precipitating, and it is to maintain Fe3+Form exist, in this way, in end processing sequences, Fe3+It can be with the square sodium of molecular sieve
Sodium ion in gabion swaps, and enters in the sodalite cage of molecular sieve.
Step 3 is post-processed, and the magnetic molecule sieve is obtained.
A kind of preferred embodiment according to the present invention, in step 3, the post-processing include separation, drying and roasting.
In further preferred embodiment, the drying carries out as follows: in air and/or nitrogen, 80~140 DEG C
4~18h of lower drying.
In embodiment still more preferably, the drying carries out as follows: in air and/or nitrogen, 100~
Dry 6~15h at 120 DEG C.
Wherein, in step 2, the Fe in soluble iron salting liquid3+With the H in molecular sieve+Ion exchange has occurred, passes through
Roasting process makes Fe3+Form Fe3O4And/or Fe, so that the magnetic behavior of molecular sieve is assigned, to improve separating property.
A kind of preferred embodiment according to the present invention, it is described to be roasted to three sections of roastings, wherein the atmosphere roasted is followed successively by
Nitrogen, oxygen and hydrogen.
In further preferred embodiment, the roasting carries out at 300~700 DEG C, is preferable over 400~600 DEG C
Lower progress, more preferably carries out at 450-550 DEG C.
In embodiment still more preferably, the roasting carries out 4~20h, preferably 8~15h of progress, such as 10h.
Wherein, calcining time is to Fe3+Migration and Fe3O4And/or the formation of Fe is most important.
A kind of preferred embodiment according to the present invention, the roasting is successively following to be carried out: roast 2 under nitrogen atmosphere~
8h roasts 2~8h under oxygen atmosphere, and 1~5h is roasted under atmosphere of hydrogen.
Wherein, the main purpose of this section roasting is to promote Fe3+To the β cage (sodalite of molecular sieve from the supercage of molecular sieve
Cage) migration.Wherein, in the present invention, the molecular sieve after nitrogen roasts is become into FeY type molecular sieve.
In further preferred embodiment, the roasting is successively following to be carried out: 4~6h is roasted under nitrogen atmosphere,
4~6h is roasted under oxygen atmosphere, and 2~4h is roasted under atmosphere of hydrogen.
Wherein, the main purpose of this section roasting is that iron ion is promoted to form Fe under oxygen atmosphere2O3。
In embodiment still more preferably, the roasting is successively following to be carried out: 4h is roasted under nitrogen atmosphere, in
4h is roasted under oxygen atmosphere, roasts 2h under atmosphere of hydrogen.
Wherein, the main purpose of this section roasting is that oxygen is promoted to roast the Fe to be formed2O3It reacts to be formed with hydrogen and there is magnetism
Fe3O4。
Wherein, the difference of calcining time has a significant impact the magnetic behavior of product under different atmosphere, specifically: (1) existing
It may advantageously facilitate Fe in nitrogen roasting process3+β cage migration into molecular sieve, when nitrogen calcining time is shorter, Fe in molecular sieve3 +The mobilance migrated to β cage is relatively low, with the extension of nitrogen calcining time, Fe3+The mobilance migrated to β cage is substantially improved；
(2) it is conducive to form the single Fe being fixed in Y molecular sieve body phase in oxygen roasting process2O3, improving the same of stability
When, by Fe3+Oxidation, exists, it is possible to reduce Fe in later period use process in the form of an oxide3O4Loss, extend magnetic molecule
The service life of sieve, wherein if calcining time is too short in oxygen, will affect Fe in molecular sieve2O3Pick-up rate；(3) hydrogen roasts
When the burning time is shorter, Fe in molecular sieve2O3Reduction degree it is relatively low, with the extension of hydrogen firing time, Fe2O3Reduction degree it is big
Width is promoted, and when reaching a certain level the hydrogen firing time, then the calcining time extended in hydrogen can cause over reduction, instead
It will affect the magnetic behavior of molecular sieve.Therefore, in the preparation process of magnetic molecule sieve, roasting is a vital step
Suddenly, the atmosphere type and calcining time that especially each firing stage uses have the magnetic behavior of obtained magnetic molecule sieve
It has a major impact.
Wherein, the H in HY type molecular sieve+With the Fe in soluble ferric iron salt3+After carrying out ion exchange, hydrated iron exists
When room temperature, it is difficult to enter in sodalite cage 1, mainly exchange in Y type molecular sieve supercage.In this application, inventor is through excessive
It is found after amount experimental study, dexterously hydrated iron can be promoted in sodalite cage (β cage) using the roasting of nitrogen atmosphere
Migration.Then it roasts once again, forms the Fe being located in sodalite cage (β cage)3O4Particle and/or Fe particle, in this way, being located at square sodium
Fe in gabion (β cage)3O4Particle and/or Fe particle are compared to the Fe in supercage3O4Particle and/or Fe particle have better
Stability is not easy.Meanwhile Fe3O4And/or Fe particle migration to sodalite cage is able to suppress zeolite skeleton dealuminzation, Ke Yizeng
The thermal stability of strong Y type molecular sieve, and supercage B acid can be offset if being positioned at supercage, i.e. Bronsted acid, and become coking center.
Another aspect of the present invention provides a kind of magnetic molecule that the method obtains according to a first aspect of the present invention sieve, institute
Stating molecular sieve is Fe3O4- Fe/Y type molecular sieve, wherein Fe has been formed in situ in Y molecular sieve3O4Particle and/or Fe particle are assigned
Molecular sieve magnetism is given, the magnetic molecule sieve is obtained, for separating.
A kind of preferred embodiment according to the present invention, the Fe3O4Particle and/or Fe particle are nanoscale.
In further preferred embodiment, the Fe3O4Particle and/or Fe particle are located at the sodalite cage of molecular sieve
In.
In embodiment still more preferably, the Fe3O4Particle is spinel structure, and the Fe particle is body-centered
Cubic structure.
Wherein, hydrated iron is in room temperature, it is difficult to enter in sodalite cage, mainly exchange in the supercage of molecular sieve.
Invention is found after lot of experiments, in the roasting process of nitrogen atmosphere, is easier to enter in sodalite cage, and incite somebody to action
Sodium ion exchange in sodalite cage is into supercage.
A kind of preferred embodiment according to the present invention, the XRD diffracting spectrum of the magnetic molecule sieve is in 2 θ=43.02 °
There is Fe at place3O4The characteristic peak of spinel structure.
In further preferred embodiment, the XRD diffracting spectrum of the magnetic molecule sieve has Fe at 2 θ=82.5 °
The characteristic peak of body-centered cubic structure.
In embodiment still more preferably, it is described magnetism modified molecular screen in XRD diffracting spectrum (220),
(311), (331) three crystal faces have characteristic peak, it is preferable that its relative intensity is I (331) > I (311) > I (220).
Wherein, Fe in the magnetic molecule sieve3O4Spinel structure and/or Fe body-centered cubic structure are obvious, and intensity is big, shape
At Fe3O4And/or Fe even particle distribution, also, Fe3O4Structure or Fe body-centered cubic structure advantages of good crystallization, regular crystal forms, tool
There is excellent magnetic behavior.
The Curie temperature of a kind of preferred embodiment according to the present invention, the magnetic molecule sieve is 500~700 DEG C.
In further preferred embodiment, the Curie temperature of the magnetic molecule sieve is 500~600 DEG C.
In embodiment still more preferably, the Curie temperature of the magnetic molecule sieve is 550 DEG C.
Wherein, the magnetic molecule sifter device has very high Curie temperature, needs far beyond most of using magnetic
Molecular sieve is the use temperature of carrier, in this way, keeping the application of the molecular sieve extremely wide.
A kind of preferred embodiment according to the present invention, saturation magnetization of the magnetic molecule sieve at 25 DEG C is 8
~12emu/g, the saturation magnetization at 100 DEG C are 7~10emu/g.
In further preferred embodiment, saturation magnetization of the magnetic molecule sieve at 25 DEG C be 9~
10emu/g, the saturation magnetization at 100 DEG C are 8~9emu/g.
Wherein, magnetic molecule to be sieved, saturation magnetization is stronger, and magnetic induction is better, and separation is more thorough, and
And the magnetism of magnetic molecule sieve be affected by temperature it is smaller.
Beneficial effect possessed by the present invention includes:
(1) the method for the invention is simple, it is easy to accomplish, operating condition is mild, and it is environmentally protective, and it is suitble to industrialized production
Using；
(2) the method for the invention uses two-step solution, it is therefore prevented that Fe (OH)3The generation of precipitating；
(3) the method for the invention successfully makes Fe using the more atmosphere roastings of multistage3+From the supercage of molecular sieve to molecular sieve
Sodalite cage migration；
(4) Fe in magnetic molecule sieve of the present invention3O4Particle and/or Fe even particle distribution, structure crystalline is good, crystal form
It is regular；
(5) magnetic molecule sieve structure of the present invention is stablized, and not easily runs off Fe in use3O4And/or Fe, thus
Long service life, effect is good, and magnetic molecule sieve can recycle.
Embodiment
The present invention is further described below by way of specific embodiment.But these embodiments are only exemplary, not
Any restrictions are constituted to protection scope of the present invention.
Embodiment 1
NaY type molecular sieve is activated into 4h at 500 DEG C, the molecular sieve for then taking 1g to activate is placed in 50mL concentration and is
In the ammonium acetate solution of 0.2mol/L, reaction is modified at 90 DEG C for 24 hours；After modification, it is filtered, washed and dried molecule
Sieve, and 4h is roasted in 500 DEG C of nitrogen atmospheres to it, obtain HY type molecular sieve.
Fe (the NO that 500mL concentration is 0.2mol/L is added in the HY type molecular sieve that 1g is obtained3)3In solution, and at 90 DEG C
Carry out ion-exchange reactions for 24 hours.
Then it is filtered, washs, the dry 12h at 100 DEG C, and nitrogen atmosphere roasts 4h at 500 DEG C, obtains FeY
Type molecular sieve, then oxygen atmosphere roasts 4h at 500 DEG C, obtains Fe2O3/ Y type molecular sieve, finally atmosphere of hydrogen roasts at 500 DEG C
2h is burnt, the magnetic molecule sieve (Fe is obtained3O4- Fe/Y type molecular sieve).
Embodiment 2
NaY type molecular sieve is activated into 4h at 500 DEG C, the molecular sieve for then taking 1g to activate is placed in 60mL concentration and is
In the chlorination amine aqueous solution of 0.1mol/L, reaction 22h is modified at 80 DEG C；After modification, it is filtered, washed and dried molecule
Sieve, and 3h is roasted in 600 DEG C of nitrogen atmospheres to it, obtain HY type molecular sieve.
The FeCl that 40mL concentration is 0.3mol/L is added in the HY type molecular sieve that 1g is obtained3In solution, and at 100 DEG C into
Row ion-exchange reactions 12h.
Then it is filtered, washs, the dry 18h at 80 DEG C, and nitrogen atmosphere roasts 6h at 450 DEG C, obtains FeY type
Molecular sieve, then oxygen atmosphere roasts 6h at 450 DEG C, obtains Fe2O3/ Y type molecular sieve, finally atmosphere of hydrogen roasts at 450 DEG C
3h obtains the magnetic molecule sieve (Fe3O4- Fe/Y type molecular sieve).
Embodiment 3
NaY type molecular sieve is activated into 3h at 550 DEG C, the molecular sieve for then taking 1g to activate is placed in 40mL concentration and is
In the ammonium acetate solution of 0.3mol/L, reaction is modified at 100 DEG C for 24 hours；After modification, it is filtered, washed and dried molecule
Sieve, and 5h is roasted in 400 DEG C of nitrogen atmospheres to it, obtain HY type molecular sieve.
The HY type molecular sieve that 1g is obtained is added in the ferrum sulfuricum oxydatum solutum that 60mL concentration is 0.1mol/L, and at 90 DEG C into
Row ion-exchange reactions is for 24 hours.
Then it is filtered, washs, dried for 24 hours at 800 DEG C, and nitrogen atmosphere roasts 4h at 550 DEG C, obtains FeY
Type molecular sieve, then oxygen atmosphere roasts 4h at 550 DEG C, obtains Fe2O3/ Y type molecular sieve, finally atmosphere of hydrogen roasts at 550 DEG C
2h is burnt, the magnetic molecule sieve (Fe is obtained3O4- Fe/Y type molecular sieve).
Embodiment 4
NaY type molecular sieve is activated into 4h at 450 DEG C, the molecular sieve for then taking 1g to activate is placed in 20mL concentration and is
In the chlorination amine aqueous solution of 0.5mol/L, reaction is modified at 60 DEG C for 24 hours；After modification, it is filtered, washed and dried molecule
Sieve, and 4h is roasted in 700 DEG C of nitrogen atmospheres to it, obtain HY type molecular sieve.
The HY type molecular sieve that 1g is obtained is added in the acetic acid ferrous solution that 45mL concentration is 0.2mol/L, and at 120 DEG C
Carry out ion-exchange reactions 8h.
Then it is filtered, washs, the dry 6h at 120 DEG C, and nitrogen atmosphere roasts 3h at 600 DEG C, obtains FeY type
Molecular sieve, then oxygen atmosphere roasts 3h at 600 DEG C, obtains Fe2O3/ Y type molecular sieve, finally atmosphere of hydrogen roasts at 600 DEG C
2h obtains the magnetic molecule sieve (Fe3O4- Fe/Y type molecular sieve).
Embodiment 5
NaY type molecular sieve is activated into 6h at 400 DEG C, the molecular sieve for then taking 1g to activate is placed in 80mL concentration and is
In the ammonium acetate solution of 0.1mol/L, reaction 12h is modified at 120 DEG C；After modification, it is filtered, washed and dried molecule
Sieve, and 6h is roasted in 300 DEG C of nitrogen atmospheres to it, obtain HY type molecular sieve.
Fe (the NO that 50mL concentration is 0.2mol/L is added in the HY type molecular sieve that 1g is obtained3)3In solution, and at 90 DEG C
Carry out ion-exchange reactions for 24 hours.
Then it is filtered, washs, the dry 4h at 140 DEG C, and nitrogen atmosphere roasts 5h at 400 DEG C, obtains FeY type
Molecular sieve, then oxygen atmosphere roasts 5h at 400 DEG C, obtains Fe2O3/ Y type molecular sieve, finally atmosphere of hydrogen roasts at 400 DEG C
3h obtains the magnetic molecule sieve (Fe3O4- Fe/Y type molecular sieve).
Comparative example
Comparative example 1
The preparation process of embodiment 1 is repeated, difference is, when roasting successively carries out as follows: prior to roasting in air atmosphere
Then 4h roasts 2h in hydrogen atmosphere, obtain the magnetic molecule sieve.
Comparative example 2
The preparation process of embodiment 1 is repeated, difference is, when roasting successively carries out as follows: prior to roasting in air atmosphere
4h roasts 4h in nitrogen atmosphere, 2h is finally roasted in hydrogen atmosphere, obtains the magnetic molecule sieve.
Comparative example 3
The preparation process of embodiment 1 is repeated, difference is, when roasting successively carries out as follows: prior to roasting in nitrogen atmosphere
4h roasts 4h in air atmosphere, 2h is finally roasted in hydrogen atmosphere, obtains the magnetic molecule sieve.
Experimental example
1 XRD diffraction experiment of experimental example
Experimental example 1-1
XRD diffraction experiment is carried out respectively to HY type molecular sieve obtained in embodiment 1 and raw material NaY type molecular sieve, XRD spreads out
Firing angle degree is 5~90 °, as a result as shown in Figure 1.
Wherein, as seen from Figure 1, NaY type molecular sieve is through ammonium acetate modified (220), (311), (331) these three crystalline substances
The relative intensity of the diffraction maximum in face does not change, and only intensity decreases, and illustrates that NaY type molecular sieve is modified through ammonium acetate
Crystal structure is not damaged afterwards.
Experimental example 1-2
To FeY type molecular sieve, Fe obtained in embodiment 12O3/ Y type molecular sieve and Fe3O4- Fe/Y type molecular sieve difference
XRD diffraction experiment is carried out, XRD angle of diffraction is 5~90 °, as a result as shown in Figure 2.
Wherein, in Fig. 2 it can be seen that
(1)Fe3O4- Fe/Y type molecular sieve is 18.24 ° (110), 30.04 ° (220), 35.38 ° (311), 43.02 ° in 2 θ
(400), occur apparent diffraction maximum at 53.42 ° (422), 56.96 ° (511), 62.52 ° (440), 83.88 ° (533), this with
The Fe of standard3O4XRD spectrum it is consistent, it can be determined that go out molecular sieve in contain spinel-type Fe3O4；
(2)Fe3O4- Fe/Y type molecular sieve is the characteristic peak for having Fe body-centered cubic structure at 82.5 ° in 2 θ, it can be determined that is gone out
Contain body-centered cubic structure Fe in molecular sieve.
Meanwhile with Fe2O3The XRD diffraction maximum of/Y type molecular sieve is compared, Fe3O4The XRD diffraction maximum phase of-Fe/Y type molecular sieve
To weaker and have apparent widthization phenomenon, this is that nanoparticle small-size effect causes.Also, the Fe of spinel-type3O4With very
Good magnetic behavior, while nanoscale size makes the magnetic behavior more stable homogeneous of molecular sieve, to not influence it
Subsequent processing is carried out as carrier.
Also, in the embodiment 1, complex chart 1 and Fig. 2, as shown in figure 3, compare the XRD spectra of NaY type molecular sieve with
FeY type molecular sieve (N2After roasting) XRD spectra, find FeY type molecular sieve XRD spectrum compared to NaY type molecular sieve occur
Peak position is whole to wide-angle diffraction angular variation, thus it is speculated that reason is: making Fe by the roasting of nitrogen atmosphere3+It is not present in
In supercage but it is present in sodalite cage, that is, is successfully realized Fe3+Migration from from supercage to sodalite cage.
Wherein, the FeY type molecular sieve refers to the molecular sieve after nitrogen atmosphere roasting.
The measurement of 2 Curie temperature of experimental example
The Fe that embodiment 1 is obtained3O4- Fe/Y type molecular sieve carries out the measurement of Curie temperature, as a result as shown in figure 4, by scheming
It can be seen that the rising with temperature, Fe in 43O4The magnetic induction intensity of-Fe/Y starts to reduce.At 550 DEG C, Fe3O4-Fe/Y
It is magnetic disappear, show superparamagnetism.As it can be seen that Fe3O4The Curie temperature of-Fe/Y is 550 DEG C.And most of needs are made
For occasion with this magnetic molecule sieve carrier, 550 DEG C considerably beyond necessary requirement.This makes Fe3O4- Fe/Y's answers
Become extremely wide with range.
The characterization of 3 hysteresis loop of experimental example
(1) Fe that embodiment 1 is obtained3O4- Fe/Y type molecular sieve (20.1mg) carries out magnetic hysteresis at 25 DEG C and 100 DEG C and returns
The characterization of line, as a result respectively as shown in Fig. 5~6, in which:
As seen from Figure 5, at 25 DEG C, Fe3O4The saturation magnetization of-Fe/Y type molecular sieve is 9.154emu/g, is rectified
Stupid power is 143Oe；
As seen from Figure 6, at 100 DEG C, Fe3O4The saturation magnetization of-Fe/Y type molecular sieve is 8.706emu/g,
Coercivity is still 143Oe.
(2) simultaneously, hysteresis loop characterization is carried out to the magnetic molecule sieve that comparative example 1~3 obtains, the results are shown in Table 1.
Table 1:
Wherein, for magnetic molecule sieve is as carrier, saturation magnetization is stronger, and magnetic induction is better, separation
It is more thorough；And coercivity is lower, then not easy to reunite, dispersibility is better.It is obtained as shown in Table 1 with its comparative example 1~3
Molecular sieve is compared, the Fe that the method obtains according to the present invention3O4- Fe/Y type molecular sieve (1 sample of embodiment) has high saturation magnetic
Change intensity and low-coercivity.
Preferred embodiment and exemplary example is combined to describe the invention in detail above.But need to state
It is that these specific embodiments are only not constitute any limit to protection scope of the present invention to illustrative explanations of the invention
System.Without departing from spirit of that invention and protection scope, the technology of the present invention content and embodiments thereof can be carried out
Various improvement, equivalencing or modification, these fall within the protection scope of the present invention.Protection scope of the present invention is with appended power
Subject to benefit requires.
Claims (10)
1. a kind of preparation method of magnetic molecule sieve, which is characterized in that the described method comprises the following steps:
Step 1 is modified molecular sieve, obtains HY type molecular sieve；
Step 2, the HY type molecular sieve that step 1 is obtained and soluble iron salting liquid carry out ion exchange；
Step 3 is post-processed, and the magnetic molecule sieve is obtained.
2. the method according to claim 1, wherein step 1 is carried out before step 1 ':
Step 1 ', molecular sieve is activated；
Preferably, the activation processing carries out at 400~600 DEG C, it is highly preferred that the activation processing is at 450-550 DEG C
It carries out, such as is carried out at 500 DEG C；
And/or
Step 1 includes following sub-step:
Step 1-1, molecular sieve is added in ammonium salt solution and is modified；
Step 1-2, it filtered, dried and is roasted after being modified, obtain HY type molecular sieve.
3. method according to claim 1 or 2, which is characterized in that in step 1-1,
The ammonium salt is selected from ammonium acetate and/or halogeno-amine, it is preferable that the ammonium salt is selected from ammonium acetate and/or ammonium chloride, more preferably
Ground, the ammonium salt are selected from ammonium acetate；And/or
The concentration of the ammonium salt solution is 0.1~0.5mol/L, preferably 0.1~0.3mol/L, more preferably 0.2mol/L；
And/or
The ratio between weight of molecular sieve and the volume of ammonium salt solution are 1:(20~80), preferably 1:(40~60), more preferably 1:
(45~55), such as 1:50；And/or
The modification carries out as follows: in 60~120 DEG C carry out 12~for 24 hours, be preferable over 80~100 DEG C carry out 18~for 24 hours, more preferably
In 90 DEG C carry out 22~for 24 hours.
4. method according to claim 1 to 3, which is characterized in that in step 1-2,
The drying carries out at 80~140 DEG C, is preferable at 100~120 DEG C and carries out；And/or
The roasting carries out at 200~800 DEG C, is preferable at 300~700 DEG C and carries out, more preferably at 400~600 DEG C into
Row.
5. method according to claim 1 to 4, which is characterized in that in step 2,
The soluble iron salting liquid includes ferric chloride solution, ferrum sulfuricum oxydatum solutum, iron nitrate solution and acetic acid ferrous solution, preferably
Ground, the soluble iron salting liquid includes ferric chloride solution and iron nitrate solution, it is highly preferred that the soluble iron salting liquid is
Iron nitrate solution；And/or
The ratio between weight of HY type molecular sieve and the volume of soluble iron salting liquid are 1:(20~80), preferably 1:(40~60),
More preferably 1:(45~55), such as 1:50；And/or
The ion exchange carries out as follows: in 60~120 DEG C of 8~30h of progress, be preferable over 80~100 DEG C carry out 12~for 24 hours, more
90 DEG C are preferable over to carry out for 24 hours.
6. method according to claim 1 to 5, which is characterized in that in step 3, it is described post-processing include separation,
Dry and roasting；
Preferably, the drying carries out as follows: in air and/or nitrogen, dry 4~18h at 80~140 DEG C, more preferably in
In air and/or nitrogen, 6~15h is dried at 100~120 DEG C.
7. according to the method described in claim 6, it is characterized in that, described be roasted to three sections of roastings, wherein the atmosphere roasted according to
Secondary is nitrogen, oxygen and hydrogen；
Preferably: the roasting carries out at 300~700 DEG C, is preferable at 400~600 DEG C and carries out, more preferably in 450-550
It is carried out at DEG C；
More preferably: the roasting carries out 4~20h, preferably 8~15h of progress, such as 10h.
8. being carried out the method according to the description of claim 7 is characterized in that the roasting is successively following: being roasted under nitrogen atmosphere
2~8h is burnt, 2~8h is roasted under oxygen atmosphere, 1~5h is roasted under atmosphere of hydrogen；Preferably, 4 are roasted under nitrogen atmosphere
~6h roasts 4~6h under oxygen atmosphere, and 2~4h is roasted under atmosphere of hydrogen；It is highly preferred that 4h is roasted under nitrogen atmosphere,
4h is roasted under oxygen atmosphere, roasts 2h under atmosphere of hydrogen.
9. a kind of magnetic molecule sieve, it is preferred to use one of claim 1 to 8 the method is made, which is characterized in that the molecule
Sieve is Fe3O4- Fe/Y type molecular sieve, wherein Fe has been formed in situ in Y molecular sieve3O4Particle and Fe particle；
Preferably, the Fe3O4Particle is spinel structure, and the Fe particle is body-centered cubic structure, and the Fe3O4Particle and
Fe particle is nanoscale；
It is highly preferred that the Fe3O4Particle and Fe particle are located in the sodalite cage of molecular sieve.
10. magnetic molecule sieve according to claim 9, which is characterized in that
The Curie temperature of the magnetic molecule sieve is 500~700 DEG C, preferably 500~600 DEG C, more preferably 550 DEG C；And/or
Saturation magnetization of the magnetic molecule sieve at 25 DEG C is 8~12emu/g, and the saturation magnetization at 100 DEG C is 7
~10emu/g, it is preferable that saturation magnetization of the magnetic molecule sieve at 25 DEG C is 9~10emu/g, full at 100 DEG C
It is 8~9emu/g with the intensity of magnetization.
Priority Applications (1)
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|---|---|---|---|
| CN201710828026.9A CN109502603B (en) | 2017-09-14 | 2017-09-14 | Preparation method of magnetic molecular sieve and obtained magnetic molecular sieve |
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