CN109092374A - A kind of preparation method of the honeycomb carrier of oxygen - Google Patents
A kind of preparation method of the honeycomb carrier of oxygen Download PDFInfo
- Publication number
- CN109092374A CN109092374A CN201811074982.3A CN201811074982A CN109092374A CN 109092374 A CN109092374 A CN 109092374A CN 201811074982 A CN201811074982 A CN 201811074982A CN 109092374 A CN109092374 A CN 109092374A
- Authority
- CN
- China
- Prior art keywords
- oxygen
- honeycomb carrier
- nitrate
- carrier
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000001301 oxygen Substances 0.000 title claims abstract description 67
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 229910052878 cordierite Inorganic materials 0.000 claims description 36
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 18
- 239000011833 salt mixture Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 description 23
- 229910001845 yogo sapphire Inorganic materials 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 238000002791 soaking Methods 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241000605159 Nitrobacter Species 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/755—Nickel
-
- B01J35/56—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
Abstract
The present invention discloses a kind of preparation method of honeycomb carrier of oxygen, and pretreated honeycomb substrate is immersed in active mixed solution, is being roasted after taking-up, and the honeycomb carrier of oxygen is made；The obtained honeycomb carrier of oxygen of the present invention is good applied to the burning of methane chemical chain, chemical chain hydrogen production by water decomposition effect, and honeycomb carrier of oxygen mechanical performance of the present invention is strong, and thermal stability is good, and compressive resistance is high, and high temperature resistant is hot, service life cycle with higher；Raw material is cheap and easy to get, process flow is simple, and solid foundation has been laid in the industrialization for chemical chain technology from now on.
Description
Technical field
The present invention relates to a kind of preparation methods of honeycomb carrier of oxygen, belong to energy fuel field.
Background technique
The energy is the important material base of human survival and development, with the increasingly depleted and environmental pollution of petroleum resources
It constantly aggravates, under sustainable development idea guidance, each state is all actively developing low-carbon economy, that is, passes through technological innovation, system
The multiple means such as innovation, industrial transformation, new energy development are reduced as far as the high-carbon energy consumption such as coal oil, reduce temperature
The discharge of room gas, reaches a kind of economic development form of socio-economic development Yu ecological environmental protection two-win.
Chemical chain burning technology is anti-burn with fuel using the Lattice Oxygen in variable valency metal oxide as oxygen source
It answers, whole process is gas-solid reaction, and reaction system is simple, and process is easily controllable, participates in reacting without gas phase oxygen, in addition, empty
Gas is to separate charging with fuel, avoids the danger of explosion.The technology of this great potential is so far still in laboratory research rank
Section, most of traditional carriers of oxygen used in overall process are powdered, and the powdered carrier of oxygen exists in amplification production
Serious deficiency, powder catalyst can be deposited in reactor bottom in use, be easy blocking reaction vessel, there is quick-fried
Fried danger, and the problems such as powder catalyst is there is being difficult to recycle, and service life cycle is low, these all limit the skill
The development of art.And the appearance of the honeycomb carrier of oxygen largely solves the above problems, and the honeycomb carrier of oxygen has energy
Enough make gas and the carrier of oxygen more fully haptoreaction, greatly improves fuel to titanium dioxide charcoal percent conversion.This is future
Realize that the amplification test of the technique, or even industrialization create solid feasible necessary condition.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation methods of honeycomb carrier of oxygen, first to cordierite
Honeycomb substrate is pre-processed, and adds water to be configured to living solution in nitrate and organic reducing agent, then by impregnating and roasting system
The honeycomb carrier of oxygen, specific preparation method the following steps are included:
(1) cordierite honeycomb carrier is entirely immersed in acid solution, guarantees that acid solution submerges cordierite honeycomb carrier upper surface,
It impregnates 10 ~ 12 hours, soak acid-cleaning can make MgO, Al in cordierite2O3、SiO2Equal ingredients dissolution falls off, and increases surface
Roughness, expand duct, convenient in conjunction with the carrier of oxygen；The cordierite honeycomb carrier that soak acid-cleaning is crossed again is washed with deionized water
It washs, washing to washing water is neutrality, is placed it in dry in baking oven；
(2) ratio for being 6:4 according to reactive metal oxides and the mass ratio of inert metal oxides calculates corresponding activity gold
Then active metal nitrate and inert metal nitrate are mixed to get mixed by the amount of genus nitrobacter and inert metal nitrate
Salt-mixture and reducing agent are mixed, add water and 3 ~ 6h is stirred at room temperature by salt, are configured to the mixing that mixing salinity is 150 ~ 250g/L
Solution；
(3) step (1) processed cordierite honeycomb carrier is immersed in the mixed solution of step (2), is taken out after 12 ~ 20h,
Blow extra solution off with ear washing bulb；
(4) cordierite honeycomb carrier of step (3) is put into Muffle furnace and is roasted, maturing temperature is 800 ~ 1200 DEG C, roasting
Burning the time is 1 ~ 3 hour, and heating rate is 5 ~ 10 DEG C/min, and the honeycomb carrier of oxygen is made.
Step (1) described acid solution is the HNO that mass fraction is 20% ~ 30%3Solution or glacial acetic acid.
Step (2) reactive metal oxides are iron oxide, nickel oxide, cobalt oxide, manganese oxide or copper oxide, the work
Property metal nitrate be ferric nitrate, nickel nitrate, cobalt nitrate, manganese nitrate or copper nitrate.
Step (2) inert metal oxides are aluminium oxide or zirconium oxide, and the inert metal nitrate is aluminum nitrate
Or zirconium nitrate.
Step (2) reducing agent is urea or citric acid, and salt-mixture and reducing agent are mixed for 1:0.8 ~ 1 according to molar ratio
It closes.
Beneficial effects of the present invention:
(1) prices of raw materials of the present invention are cheap, and preparation method is simple, and the honeycomb carrier of oxygen obtained is fired for methane chemical chain
Burning, chemical chain hydrogen production by water decomposition, catalytic methane preparing synthetic gas, activity with higher, catalytic performance is good, and has very strong machine
Tool performance, thermal stability is good, and compressive resistance is high, and high temperature resistant is hot, and service life cycle is long, and preparation method is relatively simple, can
With batch production, it is easy to industrialize, and be easily recycled, use is safer.
(2) carrier of oxygen by it is in the prior art it is powdered become the honeycomb with duct, increase gas and oxygen
The time of contact of carrier and contact area improve the conversion ratio and conversion rate of fuel gas, then more sufficiently effective
Utilize fuel.
(3) carrier of oxygen by it is in the prior art it is powdered become the honeycomb with duct, honeycomb will not be because
Air velocity is excessive and the carrier of oxygen is blown into pipeline and causes reactor plugs, and reactor is caused to burst, greatly improving
The safety for learning chain burning technology, has then stepped a step to industrialized process again.
(4) also more traditional carrier of oxygen is more convenient when being loaded the carrier of oxygen for the honeycomb carrier of oxygen of the invention, is not required to
Increase the equipment of any steady air flow.
(5) raw material of the method for the present invention is cheap and easy to get, process flow is simple, lays for the industrialization of chemical chain technology from now on
Solid foundation.
Detailed description of the invention
Fig. 1 is honeycomb Fe prepared by embodiment 12O3/Al2O3The carrier of oxygen and conventional powder Fe2O3/Al2O3The table of the carrier of oxygen
Seeing figure, (left figure is conventional powder Fe2O3/Al2O3The carrier of oxygen, right figure are honeycomb Fe prepared by embodiment 12O3/Al2O3Oxygen carries
Body)；
Fig. 2 is honeycomb Fe prepared by embodiment 12O3/Al2O3The carrier of oxygen and conventional powder Fe2O3/Al2O3The carrier of oxygen with
CH4CH after 20 circular responses4Conversion ratio and CO2The comparison diagram of selectivity.
Specific embodiment
Invention is further described in detail With reference to embodiment, but protection scope of the present invention and unlimited
In the content.
Embodiment 1
A kind of honeycomb Fe2O3/Al2O3The preparation method of the carrier of oxygen, specifically includes the following steps:
(1) pretreatment of cordierite honeycomb carrier:
The HNO of configuration quality score 20%3Commercially available cordierite honeycomb carrier is placed in HNO by solution3In solution, guarantee HNO3Solution
Cordierite honeycomb carrier upper surface is submerged, soaking time is 10 hours, and soak acid-cleaning can make MgO, Al in cordierite2O3、
SiO2Equal ingredients dissolution falls off, and increases the roughness on surface, expands duct, convenient in conjunction with the carrier of oxygen；It is again that acid is processed
Cordierite honeycomb carrier be washed with deionized, washing to washing water be neutrality；It places it in dry in baking oven；
(2) active component solution configures:
According to m (Fe2O3):m(Al2O3The quality of ferric nitrate required for the proportion of)=6:4 calculates and aluminum nitrate simultaneously weighs mixing
Salt-mixture is obtained, urea is added further according to the ratio that the molar ratio of salt-mixture and urea is 1:1, suitable deionized water is added,
It is stirred at room temperature 3 hours, configures the solution that mixing salinity is 150g/L；
(3) honeycomb substrate is impregnated:
Step (1) processed cordierite honeycomb carrier is immersed in step (2) mixed solution, is taken out after 12h, uses ear washing bulb
Blow extra solution off；
(4) it roasts:
The cordierite honeycomb carrier of step (3) is put into Muffle furnace under air conditions and is roasted, maturing temperature is 1200 DEG C,
Calcining time is 1 hour, and heating rate is 10 DEG C/min, and Fe is made2O3/Al2O3The honeycomb carrier of oxygen.
Fig. 1 is honeycomb Fe manufactured in the present embodiment2O3/Al2O3The carrier of oxygen and conventional powder Fe2O3/Al2O3The carrier of oxygen
Apparent figure, left figure are conventional powder Fe2O3/Al2O3The carrier of oxygen, right figure are honeycomb Fe manufactured in the present embodiment2O3/Al2O3Oxygen carries
Body, it can be clearly seen that the honeycomb carrier of oxygen can be with the contact area of increase gas；Fig. 2 is honeycomb prepared by embodiment 1
Fe2O3/Al2O3The carrier of oxygen and conventional powder Fe2O3/Al2O3The carrier of oxygen with the CH after 20 circular responses of methane4Conversion ratio with
And CO2The comparison diagram of selectivity, and the Fe of the two2O3/Al2O3The carrier of oxygen is identical in quality, by figure it can be seen that the present embodiment system
Standby honeycomb Fe2O3/Al2O3The carrier of oxygen is for CH4High conversion rate up to 52.5%, than conventional powder Fe2O3/Al2O3The carrier of oxygen
It is higher, for CO2Selectivity be up to 88.3%, than conventional powder Fe2O3/Al2O3The carrier of oxygen is higher, illustrates the honeycomb carrier of oxygen
It is obviously more high-efficient than the powder carrier of oxygen in the efficiency of burning chemistry chains.
Embodiment 2
A kind of honeycomb NiO/ZrO2The preparation method of the carrier of oxygen, specifically includes the following steps:
(1) pretreatment of cordierite honeycomb carrier:
The HNO of configuration quality score 30%3Solution；Commercially available cordierite honeycomb carrier is placed in above-mentioned HNO3In solution, guarantee HNO3
Solution submerges cordierite honeycomb carrier upper surface, and soaking time is about 12 hours, soak acid-cleaning can make MgO in cordierite,
Al2O3、SiO2Equal ingredients dissolution falls off, and increases the roughness on surface, expands duct, convenient in conjunction with the carrier of oxygen；It again will be at acid
The cordierite honeycomb carrier managed is washed with deionized, and washing to washing water is neutrality；It places it in dry in baking oven.
(2) active component solution configures:
According to m (NiO): m (ZrO2The proportion of)=6:4 calculates the quality of required nickel nitrate and zirconium nitrate and weighs and mixes
To salt-mixture, urea is added further according to the ratio that the molar ratio of salt-mixture and urea is 1:0.95, suitable deionized water is added,
It is stirred at room temperature 6 hours, configures the solution that mixing salinity is 200g/L；
(3) honeycomb substrate is impregnated:
Step (1) processed cordierite honeycomb carrier is immersed in step (2) mixed solution, is taken out after 18h, uses ear washing bulb
Blow extra solution off；
(4) it roasts:
The cordierite honeycomb carrier of step (3) is put into Muffle furnace under air conditions and is roasted, maturing temperature is 1000 DEG C,
Calcining time is 2 hours, and heating rate is 8 DEG C/min, and NiO/ZrO is made2The honeycomb carrier of oxygen.
The NiO/ZrO that the present embodiment is prepared2The honeycomb carrier of oxygen is to CH4High conversion rate up to 70.2%, CO2Selectivity
Up to 90.6%.
Embodiment 3
A kind of honeycomb Co3O4/ZrO2The preparation method of the carrier of oxygen, specifically includes the following steps:
(1) pretreatment of cordierite honeycomb carrier:
The HNO of configuration quality score 25%3Solution；Commercially available cordierite honeycomb carrier is placed in above-mentioned HNO3In solution, guarantee HNO3
Solution submerges cordierite honeycomb carrier upper surface, and soaking time is about 10.5 hours, and soak acid-cleaning can make in cordierite
MgO、Al2O3、SiO2Equal ingredients dissolution falls off, and increases the roughness on surface, expands duct, convenient in conjunction with the carrier of oxygen；Again will
The processed cordierite honeycomb carrier of acid is washed with deionized, and washing to washing water is neutrality；It places it in dry in baking oven.
(2) active component solution configures:
According to m (Co3O4):m(ZrO2The proportion of)=6:4 calculates the quality of required nickel nitrate and zirconium nitrate and weighs and mixes
To salt-mixture, urea is added further according to the ratio that the molar ratio of salt-mixture and urea is 1:0.9, suitable deionized water is added,
It is stirred at room temperature 6 hours, configures the solution that mixing salinity is 220g/L；
(3) honeycomb substrate is impregnated:
Step (1) processed cordierite honeycomb carrier is immersed in step (2) mixed solution, is taken out after 15h, uses ear washing bulb
Blow extra solution off；
(4) it roasts:
The cordierite honeycomb carrier of step (3) is put into Muffle furnace under air conditions and is roasted, maturing temperature is 850 DEG C,
Calcining time is 3 hours, and heating rate is 15 DEG C/min, and Co is made3O4/ZrO2The honeycomb carrier of oxygen.
The Co that the present embodiment is prepared3O4/ZrO2The honeycomb carrier of oxygen is to CH4High conversion rate up to 76.4%, CO2Selection
Property is up to 87.9%.
Embodiment 4
A kind of honeycomb CuO/Al2O3The preparation method of the carrier of oxygen, specifically includes the following steps:
(1) pretreatment of cordierite honeycomb carrier:
Commercially available cordierite honeycomb carrier is placed in pure glacial acetic acid, guarantees that glacial acetic acid submerges cordierite honeycomb carrier upper surface,
Soaking time is about 11 hours, and soak acid-cleaning can make MgO, Al in cordierite2O3、SiO2Equal ingredients dissolution falls off, and increases
The roughness on surface expands duct, convenient in conjunction with the carrier of oxygen；Again by the processed cordierite honeycomb carrier deionized water of acid
Washing, washing to washing water are neutrality；It places it in dry in baking oven；
(2) active component solution configures:
According to m (CuO): m (Al2O3The proportion of)=6:4 calculates the quality of required copper nitrate and aluminum nitrate and weighs and mixes
To salt-mixture, citric acid is added further according to the ratio that the molar ratio of salt-mixture and citric acid is 1:0.8, suitable deionization is added
Water is stirred at room temperature 5 hours, configures the solution that mixing salinity is 250g/L；
(3) honeycomb substrate is impregnated:
Step (1) processed cordierite honeycomb carrier is immersed in step (2) mixed solution, is taken out after 20h, uses ear washing bulb
Blow extra solution off；
(4) it roasts:
The cordierite honeycomb carrier of step (3) is put into Muffle furnace under air conditions and is roasted, maturing temperature is 800 DEG C,
Calcining time is 3 hours, and heating rate is 5 DEG C/min, and CuO/Al is made2O3The honeycomb carrier of oxygen.
The CuO/Al that the present embodiment is prepared2O3The honeycomb carrier of oxygen is to CH4High conversion rate up to 70.2%, carbon dioxide
Selectivity be up to 89.3%.
Claims (5)
1. a kind of preparation method of the honeycomb carrier of oxygen, which is characterized in that specifically includes the following steps:
(1) cordierite honeycomb carrier is immersed in acid solution, is impregnated 10 ~ 12 hours, then the cordierite honeycomb impregnated is carried
Body is washed with deionized, dry after washing to neutrality；
(2) ratio for being 6:4 according to reactive metal oxides and the mass ratio of inert metal oxides, by active metal nitrate
It is mixed to get salt-mixture with inert metal nitrate, salt-mixture and reducing agent are mixed, adds water and 3 ~ 6h is stirred at room temperature, be configured to
Mix the mixed solution that salinity is 150 ~ 250g/L；
(3) step (1) processed cordierite honeycomb carrier is immersed in the mixed solution of step (2), is taken out after 12 ~ 20h,
Blow extra solution off with ear washing bulb；
(4) cordierite honeycomb carrier of step (3) is roasted, maturing temperature is 800 ~ 1200 DEG C, and calcining time is 1 ~ 3 small
When, heating rate is 5 ~ 10 DEG C/min, and the honeycomb carrier of oxygen is made.
2. the preparation method of the honeycomb carrier of oxygen according to claim 1, which is characterized in that step (1) described acid solution is
The HNO that mass fraction is 20% ~ 30%3Solution or glacial acetic acid.
3. the preparation method of the honeycomb carrier of oxygen according to claim 1, which is characterized in that step (2) described active metal
Oxide is iron oxide, nickel oxide, cobalt oxide, manganese oxide or copper oxide, and the active metal nitrate is ferric nitrate, nitric acid
Nickel, cobalt nitrate, manganese nitrate or copper nitrate.
4. the preparation method of the honeycomb carrier of oxygen according to claim 1, which is characterized in that step (2) described inert metal
Oxide is aluminium oxide or zirconium oxide, and the inert metal nitrate is aluminum nitrate or zirconium nitrate.
5. the preparation method of the honeycomb carrier of oxygen according to claim 1, which is characterized in that step (2) described reducing agent is
Urea or citric acid, salt-mixture and reducing agent are the mixing of 1:0.8 ~ 1 according to molar ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811074982.3A CN109092374A (en) | 2018-09-14 | 2018-09-14 | A kind of preparation method of the honeycomb carrier of oxygen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811074982.3A CN109092374A (en) | 2018-09-14 | 2018-09-14 | A kind of preparation method of the honeycomb carrier of oxygen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109092374A true CN109092374A (en) | 2018-12-28 |
Family
ID=64866497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811074982.3A Pending CN109092374A (en) | 2018-09-14 | 2018-09-14 | A kind of preparation method of the honeycomb carrier of oxygen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109092374A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1636862A (en) * | 2004-10-12 | 2005-07-13 | 昆明理工大学 | Method of catalytically oxidizing natural gas with lattice oxygen to prepare hydrogen in molten salt |
| CN101486941A (en) * | 2009-02-17 | 2009-07-22 | 华中科技大学 | Process for preparing iron based oxygen carrier |
| CN101857458A (en) * | 2010-05-11 | 2010-10-13 | 昆明理工大学 | Preparation method of Ce-Fe-Zr combined metal oxide honeycomb ceramics type integral oxygen carrier |
| CN102133532A (en) * | 2010-12-20 | 2011-07-27 | 昆明理工大学 | Method for preparing honeycomb integrated catalyst for catalyzing partial oxidized methane to prepare synthesis gas |
| CN103204464A (en) * | 2013-03-29 | 2013-07-17 | 中国科学院广州能源研究所 | Cellular oxygen carrier chemical-looping reforming reactor |
| CN105020704A (en) * | 2015-07-30 | 2015-11-04 | 中国科学院工程热物理研究所 | Honeycomb regenerator type chemical looping combustion reactor |
| CN107488481A (en) * | 2017-09-30 | 2017-12-19 | 江苏瑞腾涂装科技有限公司 | A kind of preparation method of iron-based oxygen carrier |
-
2018
- 2018-09-14 CN CN201811074982.3A patent/CN109092374A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1636862A (en) * | 2004-10-12 | 2005-07-13 | 昆明理工大学 | Method of catalytically oxidizing natural gas with lattice oxygen to prepare hydrogen in molten salt |
| CN101486941A (en) * | 2009-02-17 | 2009-07-22 | 华中科技大学 | Process for preparing iron based oxygen carrier |
| CN101857458A (en) * | 2010-05-11 | 2010-10-13 | 昆明理工大学 | Preparation method of Ce-Fe-Zr combined metal oxide honeycomb ceramics type integral oxygen carrier |
| CN102133532A (en) * | 2010-12-20 | 2011-07-27 | 昆明理工大学 | Method for preparing honeycomb integrated catalyst for catalyzing partial oxidized methane to prepare synthesis gas |
| CN103204464A (en) * | 2013-03-29 | 2013-07-17 | 中国科学院广州能源研究所 | Cellular oxygen carrier chemical-looping reforming reactor |
| CN105020704A (en) * | 2015-07-30 | 2015-11-04 | 中国科学院工程热物理研究所 | Honeycomb regenerator type chemical looping combustion reactor |
| CN107488481A (en) * | 2017-09-30 | 2017-12-19 | 江苏瑞腾涂装科技有限公司 | A kind of preparation method of iron-based oxygen carrier |
Non-Patent Citations (2)
| Title |
|---|
| 中国有色金属工业协会: "《中国锆、铪》", 30 April 2014 * |
| 唐晓龙等: "《低温选择性催化还原NOx技术及反应机理》", 31 March 2007 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104128184B (en) | A kind of float type CoFe2O4/TiO2/ float bead composite photochemical catalyst and preparation method thereof | |
| CN108772067B (en) | Preparation method of loaded double-transition metal monoatomic ACF catalyst for degrading VOCs at normal temperature | |
| CN102513123B (en) | Rare-earth perovskite type catalyst for treating industrial waste gas as well as preparation method and application thereof | |
| CN101767021B (en) | Method for preparing p-CoO/n-CdS compound semiconductor photocatalyst | |
| CN102626640B (en) | Monolithic catalyst for low temperature oxidation of methane and preparation thereof | |
| CN103706360B (en) | A kind of Ru/BaCeO3 ammonia synthesis catalyst and preparation method thereof | |
| CN104971727B (en) | A kind of preparation method of Ni-based catalyst for hydrogen production from methane vapor reforming | |
| CN106829914A (en) | A kind of three-dimensional porous carbon negative pole material of lithium ion battery | |
| CN109675556A (en) | A kind of ruthenium catalyst and preparation method thereof for propane catalysis burning | |
| CN103055847A (en) | Manganese-based oxide catalyst used for catalytic oxidation of ethanol, and preparation method and application thereof | |
| CN106025178B (en) | It is a kind of to prepare the method for metal oxide and its application in lithium cell cathode material by template of MOF | |
| CN103447026B (en) | Wet type catalyzed oxidation manganese-based catalyst and preparation method thereof | |
| CN109351357A (en) | A kind of effective universal method for promoting perovskite catalyst catalytic performance | |
| CN106215965B (en) | The preparation and its application in oxygen reduction reaction of Fe-N-C meso-porous carbon material | |
| CN108097239B (en) | Novel coal coke carbon dioxide gasification catalyst and preparation method thereof | |
| CN109092374A (en) | A kind of preparation method of the honeycomb carrier of oxygen | |
| CN106378137A (en) | Method for preparing rice husk-based supported metal catalyst mesoporous carbon | |
| CN102260570B (en) | Mesoporous silica base molecular sieve based iron-base oxygen carrier and preparation method thereof | |
| CN102585969B (en) | Novel iron-based oxygen carrier of nuclear-free cavity structure and preparation method thereof | |
| CN103113955A (en) | Preparation method of nano porous iron-base oxygen carrier for biological oil chemical-looping hydrogen production | |
| CN111215085B (en) | Two-step solar thermochemical energy storage non-noble metal catalyst and preparation and application thereof | |
| CN103113954A (en) | Method for preparing bio-oil chemical-looping hydrogen recycled F2O3/Al2O3 oxygen carrier through ultrasonic method | |
| CN104549213B (en) | A kind of gas-fueled vehicles Catalytic methane oxidation catalyst and preparation method thereof | |
| CN103831095B (en) | A kind of monoblock type metal composite catalyst and preparation method thereof | |
| CN105020704B (en) | Honeycomb regenerator type chemical looping combustion reactor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181228 |