CN105749864A - Preparation method of high-specific-area magnetic adsorbent or magnetic catalyst support - Google Patents
Preparation method of high-specific-area magnetic adsorbent or magnetic catalyst support Download PDFInfo
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- CN105749864A CN105749864A CN201610228451.XA CN201610228451A CN105749864A CN 105749864 A CN105749864 A CN 105749864A CN 201610228451 A CN201610228451 A CN 201610228451A CN 105749864 A CN105749864 A CN 105749864A
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- adsorbent
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 239000003463 adsorbent Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004064 recycling Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000010926 purge Methods 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 7
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 claims description 7
- 229910052756 noble gas Inorganic materials 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract description 3
- 238000007885 magnetic separation Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- 238000000231 atomic layer deposition Methods 0.000 abstract 1
- 230000005389 magnetism Effects 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 19
- 239000006227 byproduct Substances 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 235000013980 iron oxide Nutrition 0.000 description 10
- 238000011068 loading method Methods 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000006004 Quartz sand Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000001048 orange dye Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 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
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- 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
- B01J23/745—Iron
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or copper
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
A preparation method of a high-specific-area magnetic adsorbent or magnetic catalyst support is provided.In the preparation method, an adsorbing material having excellent adsorbing characteristic and magnetism and the magnetic catalyst support high in specific area and easy to separate are obtained by: supporting an iron oxide on an adsorbent or catalyst support such as activated carbon and MCM-41 by atomic layer deposition technology, without affecting normal adsorbing capacity of the support and activity of a synthesized catalyst.The adsorbent prepared using the method of the invention enables the adsorbing material to be separated quickly from a solution by using a simple magnetic separation process; compared with traditional separation methods such as filtration, the method is more efficient and convenient and has minor influence on the parameters of the adsorbent itself, such as duct size and specific area.In addition, the the catalyst synthesized using the catalyst support prepared by the method enables solid catalyst separation in multi-phase reaction through magnetic separation, availability of the catalyst is improved greatly, and the recycling problem of catalysts is solved.
Description
Technical field
The present invention relates to the preparation method of a kind of magnetic adsorbent and catalyst carrier, it is adaptable to catalyst field.
Background technology
Adsorbent is generally of relatively Large ratio surface, suitable pore passage structure, it is possible to absorb some from mixed gas or liquid
Point, in life produces, play vital effect, have been widely used and chemical industry, environmental conservation, medical and health and biological work
The fields such as journey.Conventional adsorbent has silica gel, activated alumina, activated carbon, molecular sieve etc., in terms of chemical industry and environmental conservation
It is mainly used in purifying waste gas, water process etc..Along with environmental problem is on the rise, especially water resource pollution, direct harm
Human health, it would be highly desirable to solve.Utilize adsorbent to carry out water process, the micropollution element in absorption water, there is the excellent of uniqueness
Gesture, economical and efficient, convenient to operation.Activated carbon is used for water and processes existing longer history.Powder or granular pattern adsorbent table
Area is relatively big, is adsorbed in example by more being applied to, but a great problem that more difficult recovery is it to be faced, easily cause secondary pollution.
How to carry out separating and recovering also is to realize secondary to utilize, reduce the premise of cost.Traditional filtering method efficiency is low, complex procedures, also
Easily cause the loss of adsorbent.By contrast, magnetic separation method be one efficiently, separation method easily.In the last few years, can magnetic
Change and maybe more and more can be paid close attention to by people by the adsorbent of Magnetic Isolation.Magnetic adsorbent has fine dispersion degree in water,
After target affinity thing is carried out quick adsorption, utilize self magnetic can realize solid-liquid separation, well solve conventional adsorbent
The problem being difficult to reclaim, recycle.
The preparation method of existing magnetic composite adsorbent includes high-temperature decomposition, sol-gel process, chemical coprecipitation, microemulsion method
Deng.Magnetic adsorbent magnetic prepared by these methods is relatively unstable, magnetic iron oxide distribution of particles uneven, it is more difficult to control
Adsorbent magnetization degree processed.There is preparation flow simultaneously complicated, the shortcomings such as controllability is low.In patent 201310561430.6,
First Powdered Activated Carbon is soaked in salpeter solution, then carries out pretreatment by steps such as distilled water cleanings, proportional be added into
Fe2+With Fe3+In the soluble salt solutions being configured to, be simultaneously introduced compounding ingredient and dispersant, adsorb saturated after, carry out heating up, heavy
Form sediment, be aged, the operation such as washing, prepare magnetic carbon-supported catalyst.
In today that environmental problem is the most serious, explore green sustainable chemistry synthesis, develop efficient recyclable catalyst
Have become as a big research emphasis.The catalyst of many noble metals is expensive, Precious Metals Resources recycle the economy brought
Benefit is day by day notable, receives the extensive concern of people.Catalyst separates with reaction system, is the first step reclaiming catalyst,
In traditional multiphase reaction system, the separation method of traditional solid catalyst has Filtration, a centrifugal settling method etc., but these
Traditional method is required for exclusive equipment or complicated procedures of forming separates, and separation efficiency is relatively low.
The performance of catalyst is had by catalyst carrier to be affected significantly, by necessarily modifying catalyst carrier, will urge
Agent is modified to magnetic catalyst, carries out Magneto separate, can be largely fulfilled catalyst under the effect of externally-applied magnetic field
Reclaim.But existing method such as infusion process, physics cladding process etc. make catalyst comprise magnetisable material, and magnetic is the most unstable, institute
Containing magnetic iron oxide heterogeneity, technique is loaded down with trivial details, and all have impact on catalysis activity in certain degree.
Summary of the invention
For prior art magnetic instability, magnetisable material heterogeneity, operating relatively complicated shortcoming, the present invention provides a kind of profit
By the way of ald, adsorbent or catalyst carrier cover magnetic iron oxide so that it is there is magnetic.The method
Simple operation, operation is simple, and cost is relatively low, magnetisable material uniform, controllable, it is provided that have no effect on absorption and catalysis while magnetic
Performance, and automation mechanized operation can be realized, it is expected to put into large-scale production.
The high-specific surface area magnetic adsorbent of present invention offer or the preparation method of magnetic catalyst carrier, specifically comprise the following steps that
Step one: first selected carrier is placed in the ald consersion unit built voluntarily, is passed through noble gas also
Evacuation, regulation reaction chamber outlet valve is that cavity pressure controls 10～103Pa scope, by heating make carrier be in 350 DEG C～
In the range of 600 DEG C；
Step 2: the carrier put into is carried out the controlled cladding of atomic level, a concrete cycle includes following four processes:
(1) the organic precursor steam t of ferrous metal element it is continually fed into reaction chamber1Second so that it is carry out saturated with carrier surface
Absorption, functional group exchanges with carrier surface；
(2) noble gas t it is passed through2Second, until unreacted presoma completely and byproduct of reaction purging are clean；
(3) it is passed through the second precursors (oxidizing gas) t to cavity3Second, adsorb at carrier table with in the first link
The presoma in face reacts；
(4) the second link t is repeated4Second, purging unreacted reactant and by-product；
Described carrier is to have the activated carbon of large specific surface area, pure silicon molecular sieve MCM-41, Q-10, γ-Al2O3.Described
Consersion unit is the one in fixed bed, rotary bed, fluid bed.Metallo-organic compound containing Fe element is FeCp2、
Fe(thd)3、Fe2(OtBu)3、FeCl3In one.Described oxidant is O2、O3、H2O、H2O2In one, preferably oxygen
Gas, flow is 20ml/min.Described noble gas is the one in helium, nitrogen, argon.Four processes in step 2
t1-t2-t3-t4Time length is adjusted respectively according to the specific surface area size of put into carrier.
Present invention have an advantage that
High-specific surface area magnetic adsorbent or the magnetic of magnetic catalyst carrier prepared by the present invention are more stable, magnetic iron oxide
Can uniformly add on initial carrier, it is simple to adsorbent realizes separating recycling after absorption, and urges in heterogeneous catalytic reaction
The recovery of agent.Avoid the method magnetic distributing inhomogeneity such as infusion process, coprecipitation, unstable shortcoming.
The adsorptivity of magnetic adsorbent prepared by the present invention is compared with virgin sorbent, and absorption property is compared；The magnetic catalysis of synthesis
Catalyst prepared by agent carrier, its catalytic performance is the most unaffected.
The present invention prepares high-specific surface area magnetic adsorbent or magnetic catalyst carrier, and all at gas phase state, next step completes, and saves
Follow-up loaded down with trivial details processing procedure, operation is simple.
Process of the present invention all can be by automated procedures control, it is possible to achieve large-scale production, low production cost, and reacted
Journey is closed, and does not results in pollution, and byproduct of reaction etc. can all reclaim.
Accompanying drawing explanation
The adsorption experiment figure of the magnetic adsorbent prepared by Fig. 1 embodiment 1.
The XRD of the magnetic adsorbent prepared by Fig. 2 embodiment 1
The adsorption experiment figure of the magnetic adsorbent prepared by Fig. 3 embodiment 2
After magnetic catalyst prepared by Fig. 4 embodiment 6 carries out Catalysis experiments, catalyst recovery experiment figure
Detailed description of the invention
Below in conjunction with the accompanying drawings the present invention is described in more detail.Following example are carried out premised on technical solution of the present invention
Implement, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
The present embodiment provides the preparation method of a kind of high-specific surface area magnetic adsorbent, comprising the concrete steps that of the method:
Step one: be positioned in fixed bed by 0.3g activated carbon, seals reaction chamber, utilizes vacuum pump and is passed through nitrogen regulation reaction
Intracavity pressure reaches 10Pa.By the heating of reaction chamber makes the activated carbon put into be in 350 DEG C, the heating organosilane precursor containing ferrum element
Body is to 90 DEG C.
Step 2: by presoma ferrocene Fe (Cp)2Steam is passed through reaction chamber so that it is with activated carbon generation saturated surface chemical reaction,
Functional group replaces with activated carbon surface, and the gas-solid interface response time is 6000s.It is passed through inert nitrogen gas and purges out the most anti-
Answering by-product after presoma and absorption, purge time is 2000s.In addition, being passed through oxygen makes the ferrum element being fixed on carrier surface enter
Row oxidation, oxidation time is 6000s.Finally, still it is passed through nitrogen and removes residual oxidizing agent and by-product, prepare γ-Fe2O3
Loading reaches the activated carbon-Fe of 23.7%2O3Composite magnetic adsorbent.
BET physical absorption is tested: the activated carbon BET specific surface area of unsupported iron oxides is 1217.6249m2/ g, embodiment one institute
Obtain AC-γ-Fe2O3The BET specific surface area of composite magnetic adsorbent is 1102.8114m2/ g, does not reduce too much.
Absorption property: combine Fig. 1, weighs activated carbon and the 25mg of the unsupported iron oxides of 25mg respectively through prepared by said process
Magnetic adsorbent, joins preparation 10mg/L methyl orange solution, is used for carrying out adsorption experiment.Experimental result is as shown in Figure 1.Load
The absorption property of the activated carbon after ferrum oxide does not weaken.
Embodiment 2
The present embodiment provides the preparation method of a kind of high-specific surface area magnetic adsorbent, comprising the concrete steps that of the method:
Step one: by 0.3g γ-Al2O3It is positioned in fixed bed, seals reaction chamber, utilize vacuum pump and be passed through nitrogen regulation reaction
Intracavity pressure reaches 10Pa.By the heating of reaction chamber makes the γ-Al2O3 put into be in 350 DEG C, heating containing ferrum element organic before
Drive body to 90 DEG C.
Step 2: by presoma ferrocene Fe (Cp)2Steam is passed through reaction chamber so that it is with γ-Al2O3Occur saturated surface chemistry anti-
Should, functional group replaces with carrier surface, and the gas-solid interface response time is 1800s.It is passed through inert nitrogen gas to purge out not
By-product after precursors and absorption, purge time is 900s.In addition, it is passed through oxygen and makes to be fixed on the ferrum element of carrier surface
Aoxidizing, oxidation time is 1800s.Finally, still it is passed through nitrogen and removes residual oxidizing agent and by-product, prepare
γ-Fe2O3Loading reaches the γ-Al of 20.8%2O3-Fe2O3Composite magnetic adsorbent.
Absorption property: weigh the γ-Al of the unsupported iron oxides of 25mg respectively2O3With 25mg through prepared by said process
γ-Al2O3-Fe2O3Magnetic adsorbent, joins preparation 10mg/L methyl orange solution, is used for carrying out adsorption experiment.Result shows,
γ-Al2O3 after load ferrum oxide is higher to the absorption property more original γ-Al2O3 of methyl orange dye.Not only make in conjunction with Fig. 2 explanation
Adsorbent band is magnetic and is easy to separate, and improves absorption property.
Embodiment 3
The present embodiment provides the preparation method of a kind of high-specific surface area magnetic adsorbent, comprising the concrete steps that of the method:
Step one: by 1gQ10(specific surface area is 274.4108m2/ g pure silicon carrier, has certain pore passage structure, and pore volume is about
1.33cm3/ g) it is positioned in fixed bed, seal reaction chamber, in utilizing vacuum pump and being passed through nitrogen regulation reaction chamber, pressure reaches 10Pa.
By the heating of reaction chamber being made the Q put into10Being in 350 DEG C, the heating organic precursor containing ferrum element is to 90 DEG C.
Step 2: by presoma ferrocene Fe (Cp)2Steam is passed through reaction chamber so that it is with Q10There is saturated surface chemical reaction, with
Carrier surface functional group replaces, and the gas-solid interface response time is 1800s.It is passed through before inert nitrogen gas purges out unreacted
Driving by-product after body and absorption, purge time is 900s.In addition, it is passed through oxygen to make to be fixed on the ferrum element of carrier surface and carry out oxygen
Changing, oxidation time is 1800s.Finally, still it is passed through nitrogen and removes residual oxidizing agent and by-product, prepare γ-Fe2O3
Loading reaches the Q of 28.6%10-Fe2O3Composite magnetic adsorbent.
Absorption property: weigh the Q of the unsupported iron oxides of 25mg respectively10With 25mg through the Q prepared by said process10-Fe2O3Magnetic is inhaled
Attached dose, join preparation 10mg/L methyl orange solution, be used for carrying out adsorption experiment.Result shows, the Q after load ferrum oxide10
The more original Q of absorption property to methyl orange dye10Higher and band is magnetic easily separated.
Embodiment 4
The present embodiment provides the preparation method of a kind of high-specific surface area magnetic catalyst carrier, comprising the concrete steps that of the method:
Step one: be positioned in fixed bed by 0.5gMCM-41, seals reaction chamber, utilizes vacuum pump and is passed through nitrogen regulation reaction
Intracavity pressure reaches 10Pa.By the heating of reaction chamber makes the MCM-41 molecular sieve put into be in 350 DEG C, heating has containing ferrum element
Machine presoma is to 90 DEG C.
Step 2: by presoma ferrocene Fe (Cp)2Steam is passed through reaction chamber so that it is with carrier generation saturated surface chemical reaction,
Functional group replaces with molecular sieve surface, and the gas-solid interface response time is 6000s.It is passed through inert nitrogen gas and purges out the most anti-
Answering by-product after presoma and absorption, purge time is 2000s.In addition, being passed through oxygen makes the ferrum element being fixed on carrier surface enter
Row oxidation, oxidation time is 6000s.Finally, still it is passed through nitrogen and removes residual oxidizing agent and by-product, prepare MCM-41
Loading reaches the MCM-41-Fe of 21.6%2O3Composite magnetic catalyst carrier.
Embodiment 5
The present embodiment provides the preparation method of a kind of high-specific surface area magnetic catalyst carrier, comprising the concrete steps that of the method:
Step one: be positioned in fixed bed by 1g activated carbon, seals reaction chamber, utilizes vacuum pump and is passed through nitrogen regulation reaction chamber
Interior pressure reaches 10Pa.By the heating of reaction chamber makes the activated carbon put into be in 350 DEG C, the heating organic precursor containing ferrum element
To 90 DEG C.
Step 2: by presoma ferrocene Fe (Cp)2Steam is passed through reaction chamber so that it is with activated carbon generation saturated surface chemical reaction,
Functional group replaces with activated carbon surface, and the gas-solid interface response time is 6000s.It is passed through inert nitrogen gas and purges out the most anti-
Answering by-product after presoma and absorption, purge time is 2000s.In addition, being passed through oxygen makes the ferrum element being fixed on carrier surface enter
Row oxidation, oxidation time is 6000s.Finally, still it is passed through nitrogen and removes residual oxidizing agent and by-product, prepare γ-Fe2O3
Loading reaches the activated carbon-Fe of 23.7%2O3Composite magnetic adsorbent.On the magnetic catalyst carrier prepared by said method,
Precious metal palladium in load, synthesis palladium loading is the activated carbon-Fe of 5.0%2O3-Pd composite magnetic adsorbent.
Catalytic performance is tested:
Weigh the catalyst 25.3mg that said method prepares, join in the autoclave of 250ml, add reactant Nitrobenzol
11g, etoh solvent 150ml, after system is airtight, leak detection, carry out replacing 4 times with nitrogen, hydrogen respectively, begin to warm up,
When reaction temperature reaches 50 DEG C, pressurising power to 0.5MPa, response time 1h.After reaction stops, result display Nitrobenzol
Conversion ratio 86.7%, aniline selectivity 100%.
5% commercially available catalyst is carried out catalytic reaction evaluation, and other reaction condition is identical with Application Example 5.Result display nitre
Base benzene conversion ratio 80.4%, aniline selectivity 89.9%.Then understand, the magnetic iron oxide added on catalyst performance without impact.
After reaction terminates, under the effect of externally-applied magnetic field, catalyst is separated with solvent, it is achieved the quick recovery of catalyst.
Embodiment 6
The present embodiment provides the preparation method of a kind of high-specific surface area magnetic catalyst carrier, comprising the concrete steps that of the method:
Step one: by 0.3 γ-Al2O3It is positioned in fixed bed, seals reaction chamber, utilize vacuum pump and be passed through nitrogen regulation reaction
Intracavity pressure reaches 10Pa.By the heating of reaction chamber makes the γ-Al2O3 put into be in 350 DEG C, heating containing ferrum element organic before
Drive body to 90 DEG C.
Step 2: by presoma ferrocene Fe (Cp)2Steam is passed through reaction chamber so that it is with γ-Al2O3Occur saturated surface chemistry anti-
Should, functional group replaces with carrier surface, and the gas-solid interface response time is 1800s.It is passed through inert nitrogen gas to purge out not
By-product after precursors and absorption, purge time is 900s.In addition, it is passed through oxygen and makes to be fixed on the ferrum element of carrier surface
Aoxidizing, oxidation time is 1800s.Finally, still it is passed through nitrogen and removes residual oxidizing agent and by-product, prepare
γ-Fe2O3Loading reaches the γ-Al of 20.8%2O3-Fe2O3Magnetic catalyst carrier.
Catalytic performance is tested:
On the magnetic catalyst carrier prepared by said method, precious metal palladium in load, palladium loading is 6.8%, preparation
γ-Al2O3-Fe2O3-Pd magnetic coupling catalyst.
Weigh above-mentioned catalyst 63.7mg, mix with 402.5mg quartz sand, carry out the Catalytic Combustion of the propane gas of 5%, instead
Answering temperature is 500 DEG C, reacts 30min, and propane gas and dry air flow are respectively 10ml/min and 90ml/min, and propane turns
Rate reaches 100%.
Same procedure is used to prepare γ-Al2O3-Pd catalyst, palladium loading is 8.2%, weighs γ-Al2O3-Pd catalyst 51.7mg,
Quartz sand 400.5mg, carries out catalyst combustion reaction under embodiment 6 the same terms, and obtaining conversion ratio is 98.6%.Then understand, added
The magnetic iron oxide added on catalyst performance without impact.
After experiment terminates, under the effect of externally-applied magnetic field, quartz sand is separated with catalyst, it is achieved the circulation profit of catalyst
With, as shown in Figure 4.
Claims (5)
1. a high-specific surface area magnetic adsorbent or the preparation method of magnetic catalyst carrier, it is characterised in that step is as follows:
Step one: be placed in ald consersion unit by selected carrier, is passed through noble gas evacuation, regulates reaction chamber
Outlet valve makes cavity pressure control 10～103Pa, makes reaction chamber reach 350 DEG C～600 DEG C by heating；Described carrier is
There is the activated carbon of large specific surface area, pure silicon molecular sieve MCM-41, Q-10 or γ-Al2O3；
Step 2: be passed through iron content metal element organic compound steam in reaction chamber, recycling noble gas carries out purging so,
It is subsequently passed oxidizing gas and makes to be fixed on the ferrum element oxidation of carrier surface, repeat said process according to the actual requirements, until raw
Become the ferroelectric oxide layer of desired thickness；
Step 3: use Fe2(OtBu)3Or FeCl3During for presoma, Ar need to be used to process gained under hydrogen or inert atmosphere
Ferroelectric oxide layer, is translated into γ-Fe2O3。
A kind of high-specific surface area magnetic adsorbent the most as claimed in claim 1 or the preparation method of magnetic catalyst carrier, its feature exists
One in the consersion unit described in step one is fixed bed, rotary bed, fluid bed.
A kind of high-specific surface area magnetic adsorbent the most as claimed in claim 1 or the preparation method of magnetic catalyst carrier, its feature exists
It is FeCp in the metallo-organic compound containing Fe element2、Fe(thd)3、Fe2(OtBu)3、FeCl3In one.
A kind of high-specific surface area magnetic adsorbent the most as claimed in claim 1 or the preparation method of magnetic catalyst carrier, its feature exists
It is O in the oxidizing gas described in step 22、O3、H2O、H2O2In one, flow is 20ml/min.
A kind of high-specific surface area magnetic adsorbent the most as claimed in claim 1 or the preparation method of magnetic catalyst carrier, its feature exists
One in the noble gas described in step 2 is helium, nitrogen, argon.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112221524A (en) * | 2020-09-16 | 2021-01-15 | 西安近代化学研究所 | Preparation method of supported gallium nitride catalyst with large specific surface area |
| CN112221524B (en) * | 2020-09-16 | 2023-01-13 | 西安近代化学研究所 | Preparation method of supported gallium nitride catalyst with large specific surface area |
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Inventor after: Feng Hao Inventor after: Zhang Wangle Inventor after: Qin Lijun Inventor after: Gong Ting Inventor after: Yan Ning Inventor after: Li Jianguo Inventor after: Huang Yu Inventor after: Hui Longfei Inventor before: Zhang Wangle Inventor before: Feng Hao Inventor before: Qin Lijun Inventor before: Gong Ting Inventor before: Yan Ning Inventor before: Li Jianguo Inventor before: Huang Yu Inventor before: Hui Longfei |