CN102925245A - Thermal storage oxygen carrier of core-shell structure and preparation method thereof - Google Patents
Thermal storage oxygen carrier of core-shell structure and preparation method thereof Download PDFInfo
- Publication number
- CN102925245A CN102925245A CN2012104431426A CN201210443142A CN102925245A CN 102925245 A CN102925245 A CN 102925245A CN 2012104431426 A CN2012104431426 A CN 2012104431426A CN 201210443142 A CN201210443142 A CN 201210443142A CN 102925245 A CN102925245 A CN 102925245A
- Authority
- CN
- China
- Prior art keywords
- oxygen carrier
- suspension liquid
- preparation
- ctab
- accumulating type
- 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.)
- Granted
Links
- 239000001301 oxygen Substances 0.000 title claims abstract description 65
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 65
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011258 core-shell material Substances 0.000 title abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 48
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 230000008859 change Effects 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000012876 carrier material Substances 0.000 claims abstract description 11
- 239000013049 sediment Substances 0.000 claims abstract description 11
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [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 abstract description 9
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- 238000009825 accumulation Methods 0.000 claims description 18
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 16
- 229960004756 ethanol Drugs 0.000 claims description 16
- 239000004005 microsphere Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 150000002926 oxygen Chemical class 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000011232 storage material Substances 0.000 abstract 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 238000005338 heat storage Methods 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- OWXLRKWPEIAGAT-UHFFFAOYSA-N [Mg].[Cu] Chemical compound [Mg].[Cu] OWXLRKWPEIAGAT-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention provides a thermal storage oxygen carrier of a core-shell structure and a preparation method thereof. The oxygen carrier is of a double-shell structure, namely a high-temperature phase change heat storage material. An inner shell is TiO2, and an outer shell is made of an oxygen carrier material. The method includes that the high-temperature phase change heat storage material is ground to nanoscale microballoons and dispersed in a mixed liquor of cetyl trimethyl ammonium bromide (CTAB) and ethanol to form turbid liquid, the turbid liquid and ammonia water parallelly flow and are dropped into tetra-n-butyl titanate (TBOT) slowly, a nitrate and aluminum nitrate solution is dropped into the turbid liquid gradually, stirring is conducted continuously in a dropping process, and sediment is generated; and then centrifugal processing is conducted, the sediment is washed through absolute ethyl alcohol and deionized water, the sediment is dried and baked, and the thermal storage oxygen carrier is obtained. The structure is favorable for protecting and fixing an inner-core thermal storage material becoming liquid at high temperature. Simultaneously, a frit reaction is prevented from happening between the inner-core thermal storage material and the outermost-layer oxygen carrier material, and the mechanical strength of the oxygen carrier is improved. The preparation method is simple and easy to control.
Description
Technical field
The present invention relates to a kind of nucleocapsid structure heat accumulating type oxygen carrier and preparation method thereof, belong to high efficiency of energy clean utilization field.
Background technology
Chemical chain burning technology is a kind of novel, combustion technology with distinct energy-saving and emission-reduction characteristic, and it has CO
2Interior separating property need not to add CO
2Tripping device can be caught and be obtained highly purified CO
2Gas.Burning chemistry chains utilizes the high-grade energy in the burning chemistry chains system, has realized the cascade utilization of energy, has improved Energy efficiency.This mode need not burning with separate two processes in a large number power consumption, separate and reclaim CO
2Do not need extra energy consumption, can not reduce system efficiency, reclaiming CO
2Have overwhelming superiority with the aspect of control NOx.
Chemical chain burning technology and relevant expansion application thereof are that a kind of energy conversion of novelty utilizes system, has good development prospect, along with the mankind to the demand of clean energy and the environmental requirement of increasingly stringent, be expected to develop into a kind of burning process of clean and effective of main flow.
Oxygen carrier also plays a part transferring heat in the circulating transfer oxygen between air reactor and fuel reactor.Oxygen carrier takes the heat that absorbs in the air reactor in the fuel reactor to, and these heats help to keep fuel reactor and move continuously.But regardless of oxygen carrier bed in fuel reactor or air reactor the even phenomenon of temperature distributing disproportionation is being arranged laterally and axially, particularly in air reactor, producing owing to heat release acutely also has focus.The thermal shock effect of temperature instability generation and the appearance of focus all can be accelerated fragmentation and the sintering of oxygen carrier, are unfavorable for the Systems balanth operation.
Summary of the invention
The present invention is compound to both functions heat accumulating type oxygen carrier for preparing together a kind of nucleocapsid structure and preparation method thereof on oxygen carrier and high-temperature phase change heat accumulation investigation of materials basis.
The present invention realizes by following technical proposal: a kind of nucleocapsid structure heat accumulating type oxygen carrier, this oxygen carrier are bivalve layer structure, and namely nuclear is the high-temperature phase change heat accumulation material, and inner shell is TiO
2, outer shell is the oxygen carrier material.
The high-temperature phase change heat accumulation material is carbonate or the muriate of alkaline-earth metal or is a kind of metal in aluminium, copper, silicon, the magnesium or the alloy of several compositions.
Outer shell is traditional oxygen carrier, i.e. the oxide compound of iron, cobalt, nickel, copper, chromium, manganese.TiO wherein
2Layer is conducive to the liquid heat-storing material under the fixing high temperature, prevents heat-storing material and oxygen carrier storeroom generation frit reaction, and has improved the intensity of oxygen carrier.
Another object of the present invention is to provide a kind of preparation method of nucleocapsid structure heat accumulating type oxygen carrier, following each step of process:
(1) grinds the high-temperature phase change heat accumulation material to the nano level microballoon;
The nano level microballoon is the microballoon of 1～500nm in the described step (1).
The high-temperature phase change heat accumulation material is carbonate or the muriate of alkaline-earth metal or is a kind of metal in aluminium, copper, silicon, the magnesium or the alloy of several compositions in the described step (1).
Described metal is.
(2) Nano microsphere with step (1) is scattered in the CTAB(cetyl trimethylammonium bromide by 1～10g/mL) and the mixed solution of ethanol in form suspension liquid, this suspension liquid is stirred under Ultrasonic Conditions, Nano microsphere is dispersed in the solution;
CTAB in the described step (2) and the mixed solution of ethanol are that CTAB is dissolved in the dehydrated alcohol, and the concentration that makes CTAB in the mixing solutions is 0.08～0.25mol/L.
(3) with step (2) gained suspension liquid under agitation condition, with ammoniacal liquor together and stream slowly be added dropwise to the TBOT(butyl (tetra) titanate) in, to suspension liquid pH value=9～11;
(4) nitrate and the aluminum nitrate mass ratio by 3 ︰ 2 is dissolved in the deionized water, the concentration that makes salt is 0.5～2mol/L;
Nitrate in the described step (4) refers to the nitrate of iron, cobalt, nickel, copper, chromium, manganese.
(5) solution of under 70 ℃ step (4) being prepared dropwise joins in step (3) the gained suspension liquid, continues in the dropping process to stir, and generates throw out;
The solution dripping quantity of described step (5) and the volume ratio of suspension liquid are 1 ︰ 1.
(6) step (5) gained throw out is carried out centrifugal treating, and successively with dehydrated alcohol and deionized water washing sediment, with throw out dry 12～24h at ambient temperature, then with dry 6～12h in 110～120 ℃;
(7) with the dried material of step (6) through 550～950 ℃ of roasting 2～6h, namely get nucleocapsid structure heat accumulating type oxygen carrier.
The present invention proposes oxygen carrier and two functions of accumulation of heat are combined, and constructs the functionalization oxygen carrier of nucleocapsid structure.That is, shell is the oxygen carrier material, and kernel is heat-storing material, and both are middle with TiO
2Layer separates.Oxygen carrier is finished oxygen carrier and accumulation of heat when circulating between air and fuel reactor.The heat accumulating type oxygen carrier is realized oxygen and heat transfer simultaneously in the burning chemistry chains process, can solve in the burning chemistry chains process fixed-bed reactor exists the oxygen carrier bed temperature uneven and be prone between focus and two reactors problem such as heat exchange difficulty, the original position heat exchange between the realization response device.This oxygen carrier has significant effect in the burning chemistry chains application facet, and this oxygen carrier possesses good accumulation of heat and oxygen carrying capability simultaneously.
The advantage that the present invention possesses and effect: method proposed by the invention is prepared the structure with bivalve layer; this structure is conducive to protect and fixedly becomes liquid kernel heat-storing material under the high temperature; prevent simultaneously kernel heat-storing material and outermost layer oxygen carrier storeroom generation frit reaction; this is that monoshell layer structure is not available, and has improved the physical strength of oxygen carrier.And the preparation method is simple, and is easy to control.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1
(1) uses ball mill grinding Na
2CO
3Nano level microballoon to 300nm;
(2) Nano microsphere with step (1) is scattered in the CTAB(cetyl trimethylammonium bromide by 5g/mL) and the mixed solution of ethanol in form suspension liquid, this suspension liquid is stirred under Ultrasonic Conditions, Nano microsphere is dispersed in the solution; Wherein, the mixed solution of CTAB and ethanol is that CTAB is dissolved in the dehydrated alcohol, and the concentration that makes CTAB in the mixing solutions is 0.15mol/L;
(3) with step (2) gained suspension liquid under agitation condition, with ammoniacal liquor together and stream slowly be added dropwise to the TBOT(butyl (tetra) titanate) in, to suspension liquid pH value=9;
(4) iron nitrate and the aluminum nitrate mass ratio by 3 ︰ 2 is dissolved in the deionized water, the concentration that makes salt is 0.5mol/L;
(5) solution of under 70 ℃ water bath condition step (4) being prepared is that 1 ︰ 1 dropwise joins in step (3) the gained suspension liquid by volume, continues in the dropping process to stir, and generates throw out;
(6) step (5) gained throw out is carried out centrifugal treating, and successively with dehydrated alcohol and deionized water washing sediment, with throw out dry 12h at ambient temperature, then place thermostatic drying chamber with 110 ℃ of dry 12h;
(7) with the dried material of step (6) through 750 ℃ of roasting 2h, namely get nucleocapsid structure heat accumulating type oxygen carrier.This oxygen carrier is bivalve layer structure, and namely nuclear is the high-temperature phase change heat accumulation material, and inner shell is TiO
2, outer shell is the oxygen carrier material.
Embodiment 2
(1) the nano level microballoon of usefulness ball mill grinding sodium-chlor to 1～100nm;
(2) Nano microsphere with step (1) is scattered in the CTAB(cetyl trimethylammonium bromide by 1g/mL) and the mixed solution of ethanol in form suspension liquid, this suspension liquid is stirred under Ultrasonic Conditions, Nano microsphere is dispersed in the solution; Wherein, the mixed solution of CTAB and ethanol is that CTAB is dissolved in the dehydrated alcohol, and the concentration that makes CTAB in the mixing solutions is 0.25mol/L;
(3) with step (2) gained suspension liquid under agitation condition, with ammoniacal liquor together and stream slowly be added dropwise to the TBOT(butyl (tetra) titanate) in, to suspension liquid pH value=10;
(4) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and the aluminum nitrate mass ratio by 3 ︰ 2 is dissolved in the deionized water, the concentration that makes salt is 1mol/L;
(5) solution of under 70 ℃ water bath condition step (4) being prepared is that 1 ︰ 1 dropwise joins in step (3) the gained suspension liquid by volume, continues in the dropping process to stir, and generates throw out;
(6) step (5) gained throw out is carried out centrifugal treating, and successively with dehydrated alcohol and deionized water washing sediment 3 times, with throw out dry 13h at ambient temperature, then place thermostatic drying chamber with 115 ℃ of dry 10h;
(7) with the dried material of step (6) through 550 ℃ of roasting 6h, namely get nucleocapsid structure heat accumulating type oxygen carrier.This oxygen carrier is bivalve layer structure, and namely nuclear is the high-temperature phase change heat accumulation material, and inner shell is TiO
2, outer shell is the oxygen carrier material.
Embodiment 3
(1) the nano level microballoon of usefulness ball mill grinding aluminum silicon alloy to 400～500nm;
(2) Nano microsphere with step (1) is scattered in the CTAB(cetyl trimethylammonium bromide by 10g/mL) and the mixed solution of ethanol in form suspension liquid, this suspension liquid is stirred under Ultrasonic Conditions, Nano microsphere is dispersed in the solution; Wherein, the mixed solution of CTAB and ethanol is that CTAB is dissolved in the dehydrated alcohol, and the concentration that makes CTAB in the mixing solutions is 0.08mol/L;
(3) with step (2) gained suspension liquid under agitation condition, with ammoniacal liquor together and stream slowly be added dropwise to the TBOT(butyl (tetra) titanate) in, to suspension liquid pH value=11;
(4) nickelous nitrate and the aluminum nitrate mass ratio by 3 ︰ 2 is dissolved in the deionized water, the concentration that makes salt is 2mol/L;
(5) solution of under 70 ℃ water bath condition step (4) being prepared is that 1 ︰ 1 dropwise joins in step (3) the gained suspension liquid by volume, continues in the dropping process to stir, and generates throw out;
(6) step (5) gained throw out is carried out centrifugal treating, and successively with dehydrated alcohol and deionized water washing sediment, with throw out dry 24h at ambient temperature, then place thermostatic drying chamber with 120 ℃ of dry 6h;
(7) with the dried material of step (6) through 950 ℃ of roasting 4h, namely get nucleocapsid structure heat accumulating type oxygen carrier.This oxygen carrier is bivalve layer structure, and namely nuclear is the high-temperature phase change heat accumulation material, and inner shell is TiO
2, outer shell is the oxygen carrier material.
Embodiment 4
(1) the nano level microballoon of usefulness ball mill grinding magnesium to 100～300nm;
(2) Nano microsphere with step (1) is scattered in the CTAB(cetyl trimethylammonium bromide by 8g/mL) and the mixed solution of ethanol in form suspension liquid, this suspension liquid is stirred under Ultrasonic Conditions, Nano microsphere is dispersed in the solution; Wherein, the mixed solution of CTAB and ethanol is that CTAB is dissolved in the dehydrated alcohol, and the concentration that makes CTAB in the mixing solutions is 0.1mol/L;
(3) with step (2) gained suspension liquid under agitation condition, with ammoniacal liquor together and stream slowly be added dropwise to the TBOT(butyl (tetra) titanate) in, to suspension liquid pH value=9～11;
(4) cupric nitrate and the aluminum nitrate mass ratio by 3 ︰ 2 is dissolved in the deionized water, the concentration that makes salt is 1mol/L;
(5) solution of under 70 ℃ water bath condition step (4) being prepared is that 1 ︰ 1 dropwise joins in step (3) the gained suspension liquid by volume, continues in the dropping process to stir, and generates throw out;
(6) step (5) gained throw out is carried out centrifugal treating, and successively with dehydrated alcohol and deionized water washing sediment, with throw out dry 18h at ambient temperature, then place thermostatic drying chamber with 120 ℃ of dry 8h;
(7) with the dried material of step (6) through 650 ℃ of roasting 6h, namely get nucleocapsid structure heat accumulating type oxygen carrier.This oxygen carrier is bivalve layer structure, and namely nuclear is the high-temperature phase change heat accumulation material, and inner shell is TiO
2, outer shell is the oxygen carrier material.
Embodiment 5
(1) the nano level microballoon of usefulness ball mill grinding copper-magnesium alloy to 400～500nm;
(2) Nano microsphere with step (1) is scattered in the CTAB(cetyl trimethylammonium bromide by 10g/mL) and the mixed solution of ethanol in form suspension liquid, this suspension liquid is stirred under Ultrasonic Conditions, Nano microsphere is dispersed in the solution; Wherein, the mixed solution of CTAB and ethanol is that CTAB is dissolved in the dehydrated alcohol, and the concentration that makes CTAB in the mixing solutions is 0.08mol/L;
(3) with step (2) gained suspension liquid under agitation condition, with ammoniacal liquor together and stream slowly be added dropwise to the TBOT(butyl (tetra) titanate) in, to suspension liquid pH value=11;
(4) chromium nitrate and the aluminum nitrate mass ratio by 3 ︰ 2 is dissolved in the deionized water, the concentration that makes salt is 2mol/L;
(5) solution of under 70 ℃ water bath condition step (4) being prepared is that 1 ︰ 1 dropwise joins in step (3) the gained suspension liquid by volume, continues in the dropping process to stir, and generates throw out;
(6) step (5) gained throw out is carried out centrifugal treating, and successively with dehydrated alcohol and deionized water washing sediment, with throw out dry 24h at ambient temperature, then place thermostatic drying chamber with 120 ℃ of dry 6h;
(7) with the dried material of step (6) through 950 ℃ of roasting 4h, namely get nucleocapsid structure heat accumulating type oxygen carrier.This oxygen carrier is bivalve layer structure, and namely nuclear is the high-temperature phase change heat accumulation material, and inner shell is TiO
2, outer shell is the oxygen carrier material.
Embodiment 6
(1) the nano level microballoon of usefulness ball mill grinding KCl to 100～300nm;
(2) Nano microsphere with step (1) is scattered in the CTAB(cetyl trimethylammonium bromide by 8g/mL) and the mixed solution of ethanol in form suspension liquid, this suspension liquid is stirred under Ultrasonic Conditions, Nano microsphere is dispersed in the solution; Wherein, the mixed solution of CTAB and ethanol is that CTAB is dissolved in the dehydrated alcohol, and the concentration that makes CTAB in the mixing solutions is 0.1mol/L;
(3) with step (2) gained suspension liquid under agitation condition, with ammoniacal liquor together and stream slowly be added dropwise to the TBOT(butyl (tetra) titanate) in, to suspension liquid pH value=9～11;
(4) cupric nitrate and the aluminum nitrate mass ratio by 3 ︰ 2 is dissolved in the deionized water, the concentration that makes salt is 1mol/L;
(5) solution of under 70 ℃ water bath condition step (4) being prepared is that 1 ︰ 1 dropwise joins in step (3) the gained suspension liquid by volume, continues in the dropping process to stir, and generates throw out;
(6) step (5) gained throw out is carried out centrifugal treating, and successively with dehydrated alcohol and deionized water washing sediment, with throw out dry 18h at ambient temperature, then place thermostatic drying chamber with 120 ℃ of dry 8h;
(7) with the dried material of step (6) through 650 ℃ of roasting 6h, namely get nucleocapsid structure heat accumulating type oxygen carrier.This oxygen carrier is bivalve layer structure, and namely nuclear is the high-temperature phase change heat accumulation material, and inner shell is TiO
2, outer shell is the oxygen carrier material.
Claims (7)
1. nucleocapsid structure heat accumulating type oxygen carrier, it is characterized in that: this oxygen carrier is bivalve layer structure, and namely nuclear is the high-temperature phase change heat accumulation material, and inner shell is TiO
2, outer shell is the oxygen carrier material.
2. the preparation method of a nucleocapsid structure heat accumulating type oxygen carrier is characterized in that through following each step:
(1) grinds the high-temperature phase change heat accumulation material to the nano level microballoon;
(2) Nano microsphere of step (1) is scattered in by 1～10g/mL in the mixed solution of CTAB and ethanol and forms suspension liquid, this suspension liquid is stirred under Ultrasonic Conditions, Nano microsphere is dispersed in the solution;
(3) with step (2) gained suspension liquid under agitation condition, with ammoniacal liquor together and stream slowly be added dropwise among the TBOT, to suspension liquid pH value=9～11;
(4) nitrate and the aluminum nitrate mass ratio by 3 ︰ 2 is dissolved in the deionized water, the concentration that makes salt is 0.5～2mol/L;
(5) solution of under 70 ℃ step (4) being prepared dropwise joins in step (3) the gained suspension liquid, continues in the dropping process to stir, and generates throw out;
(6) step (5) gained throw out is carried out centrifugal treating, and successively with dehydrated alcohol and deionized water washing sediment, with throw out dry 12～24h at ambient temperature, then with dry 6～12h in 110～120 ℃;
(7) with the dried material of step (6) through 550～950 ℃ of roasting 2～6h, namely get nucleocapsid structure heat accumulating type oxygen carrier.
3. the preparation method of nucleocapsid structure heat accumulating type oxygen carrier according to claim 2 is characterized in that: the nano level microballoon is the microballoon of 1～500nm in the described step (1).
4. the preparation method of nucleocapsid structure heat accumulating type oxygen carrier according to claim 2 is characterized in that: the high-temperature phase change heat accumulation material is carbonate or the muriate of alkaline-earth metal or is a kind of metal in aluminium, copper, silicon, the magnesium or the alloy of several compositions in the described step (1).
5. the preparation method of nucleocapsid structure heat accumulating type oxygen carrier according to claim 2, it is characterized in that: the CTAB in the described step (2) and the mixed solution of ethanol are that CTAB is dissolved in the dehydrated alcohol, and the concentration that makes CTAB in the mixing solutions is 0.08～0.25mol/L.
6. the preparation method of nucleocapsid structure heat accumulating type oxygen carrier according to claim 2, it is characterized in that: the nitrate in the described step (4) refers to the nitrate of iron, cobalt, nickel, copper, chromium, manganese.
7. the preparation method of nucleocapsid structure heat accumulating type oxygen carrier according to claim 2, it is characterized in that: the solution dripping quantity of described step (5) and the volume ratio of suspension liquid are 1 ︰ 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210443142.6A CN102925245B (en) | 2012-11-08 | 2012-11-08 | Thermal storage oxygen carrier of core-shell structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210443142.6A CN102925245B (en) | 2012-11-08 | 2012-11-08 | Thermal storage oxygen carrier of core-shell structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102925245A true CN102925245A (en) | 2013-02-13 |
| CN102925245B CN102925245B (en) | 2014-09-03 |
Family
ID=47640177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210443142.6A Expired - Fee Related CN102925245B (en) | 2012-11-08 | 2012-11-08 | Thermal storage oxygen carrier of core-shell structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102925245B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418097A (en) * | 2015-12-23 | 2016-03-23 | 云南泛亚能源科技有限公司 | Refractory lining material and preparation method thereof |
| CN105482668A (en) * | 2015-12-23 | 2016-04-13 | 云南泛亚能源科技有限公司 | Heating furnace heat resistant and anticorrosive coating and preparation method thereof |
| CN105797659A (en) * | 2016-04-08 | 2016-07-27 | 东南大学 | Preparation method of silicon dioxide and chitosan double-shell heat storage microcapsule |
| CN105855537A (en) * | 2016-03-24 | 2016-08-17 | 中国科学院上海应用物理研究所 | Inorganic nonmetal cladding high-temperature phase change heat storage microcapsule and preparation method thereof |
| CN106367035A (en) * | 2016-09-14 | 2017-02-01 | 昆明理工大学 | Preparing method of high-temperature phase change heat storage material of core-shell structure |
| CN106916573A (en) * | 2017-03-06 | 2017-07-04 | 中国科学院化学研究所 | Metal and alloy phase change accumulation energy microcapsule and preparation method thereof |
| CN109054758A (en) * | 2018-06-21 | 2018-12-21 | 昆明理工大学 | A kind of preparation method of the high-temperature phase change heat accumulation material of core-shell structure |
| CN109054754A (en) * | 2018-06-21 | 2018-12-21 | 昆明理工大学 | A kind of core-shell structure Fe2O3-Al2O3The preparation method of/(Al@C) the high temperature composite phase-change heat-storage carrier of oxygen |
| CN109054755A (en) * | 2018-06-21 | 2018-12-21 | 昆明理工大学 | A kind of core-shell structure Fe2O3-CeO2The preparation method of/(Al@C) the heat accumulating type carrier of oxygen |
| US10618808B2 (en) | 2014-12-17 | 2020-04-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Catalyst support, recycle reactor and method for releasing hydrogen |
| CN111378511A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Biomass microwave gasification utilization method and system |
| WO2020173089A1 (en) * | 2019-02-25 | 2020-09-03 | 苏斌 | Catalytic phase change dielectric sphere for methanol combustion and preparation method therefor |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824353A (en) * | 2010-05-04 | 2010-09-08 | 昆明理工大学 | Composite oxygen carrier for heat accumulating type chemical chain burning technology and preparation method thereof |
| CN102154051A (en) * | 2011-01-26 | 2011-08-17 | 华中科技大学 | Preparation method of CaSO4 compound oxygen carrier with nuclear shell structure |
| CN102166532A (en) * | 2010-05-04 | 2011-08-31 | 昆明理工大学 | Heat-storing catalytic composite functional material and preparation method thereof |
| CN102382706A (en) * | 2011-08-30 | 2012-03-21 | 华北电力大学 | Cavity structure TiO2 based Fe-based oxygen carrier and its preparation method |
| CN102533391A (en) * | 2012-02-16 | 2012-07-04 | 华北电力大学 | Novel iron-based oxygen carrier with interlayer shell structure, and preparation method for novel iron-based oxygen carrier |
| CN102585969A (en) * | 2012-02-16 | 2012-07-18 | 华北电力大学 | Novel iron-based oxygen carrier of nuclear-free cavity structure and preparation method thereof |
-
2012
- 2012-11-08 CN CN201210443142.6A patent/CN102925245B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824353A (en) * | 2010-05-04 | 2010-09-08 | 昆明理工大学 | Composite oxygen carrier for heat accumulating type chemical chain burning technology and preparation method thereof |
| CN102166532A (en) * | 2010-05-04 | 2011-08-31 | 昆明理工大学 | Heat-storing catalytic composite functional material and preparation method thereof |
| CN102154051A (en) * | 2011-01-26 | 2011-08-17 | 华中科技大学 | Preparation method of CaSO4 compound oxygen carrier with nuclear shell structure |
| CN102382706A (en) * | 2011-08-30 | 2012-03-21 | 华北电力大学 | Cavity structure TiO2 based Fe-based oxygen carrier and its preparation method |
| CN102533391A (en) * | 2012-02-16 | 2012-07-04 | 华北电力大学 | Novel iron-based oxygen carrier with interlayer shell structure, and preparation method for novel iron-based oxygen carrier |
| CN102585969A (en) * | 2012-02-16 | 2012-07-18 | 华北电力大学 | Novel iron-based oxygen carrier of nuclear-free cavity structure and preparation method thereof |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10618808B2 (en) | 2014-12-17 | 2020-04-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Catalyst support, recycle reactor and method for releasing hydrogen |
| CN105482668A (en) * | 2015-12-23 | 2016-04-13 | 云南泛亚能源科技有限公司 | Heating furnace heat resistant and anticorrosive coating and preparation method thereof |
| CN105418097B (en) * | 2015-12-23 | 2018-06-29 | 云南清朗能源科技有限公司 | Refractory lining material and preparation method thereof |
| CN105418097A (en) * | 2015-12-23 | 2016-03-23 | 云南泛亚能源科技有限公司 | Refractory lining material and preparation method thereof |
| CN105855537A (en) * | 2016-03-24 | 2016-08-17 | 中国科学院上海应用物理研究所 | Inorganic nonmetal cladding high-temperature phase change heat storage microcapsule and preparation method thereof |
| CN105797659A (en) * | 2016-04-08 | 2016-07-27 | 东南大学 | Preparation method of silicon dioxide and chitosan double-shell heat storage microcapsule |
| CN105797659B (en) * | 2016-04-08 | 2018-12-14 | 东南大学 | A kind of preparation method of silica chitosan bivalve heat accumulation microcapsules |
| CN106367035B (en) * | 2016-09-14 | 2019-06-11 | 昆明理工大学 | A kind of preparation method of the high-temperature phase change heat accumulation material of core-shell structure |
| CN106367035A (en) * | 2016-09-14 | 2017-02-01 | 昆明理工大学 | Preparing method of high-temperature phase change heat storage material of core-shell structure |
| CN106916573A (en) * | 2017-03-06 | 2017-07-04 | 中国科学院化学研究所 | Metal and alloy phase change accumulation energy microcapsule and preparation method thereof |
| CN106916573B (en) * | 2017-03-06 | 2019-10-29 | 中国科学院化学研究所 | Metal and alloy phase change accumulation energy microcapsule and preparation method thereof |
| CN109054755A (en) * | 2018-06-21 | 2018-12-21 | 昆明理工大学 | A kind of core-shell structure Fe2O3-CeO2The preparation method of/(Al@C) the heat accumulating type carrier of oxygen |
| CN109054754A (en) * | 2018-06-21 | 2018-12-21 | 昆明理工大学 | A kind of core-shell structure Fe2O3-Al2O3The preparation method of/(Al@C) the high temperature composite phase-change heat-storage carrier of oxygen |
| CN109054758A (en) * | 2018-06-21 | 2018-12-21 | 昆明理工大学 | A kind of preparation method of the high-temperature phase change heat accumulation material of core-shell structure |
| CN109054754B (en) * | 2018-06-21 | 2020-10-27 | 昆明理工大学 | Core-shell structure Fe2O3-Al2O3Preparation method of (Al @ C) high-temperature composite phase-change heat-storage oxygen carrier |
| CN109054755B (en) * | 2018-06-21 | 2020-10-27 | 昆明理工大学 | Core-shell structure Fe2O3-CeO2Preparation method of heat storage type oxygen carrier |
| CN109054758B (en) * | 2018-06-21 | 2020-10-27 | 昆明理工大学 | Preparation method of high-temperature phase change heat storage material with core-shell structure |
| CN111378511A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Biomass microwave gasification utilization method and system |
| CN111378511B (en) * | 2018-12-28 | 2021-05-04 | 中国石油化工股份有限公司 | Biomass microwave gasification utilization method and system |
| WO2020173089A1 (en) * | 2019-02-25 | 2020-09-03 | 苏斌 | Catalytic phase change dielectric sphere for methanol combustion and preparation method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102925245B (en) | 2014-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102925245B (en) | Thermal storage oxygen carrier of core-shell structure and preparation method thereof | |
| CN104128184B (en) | A kind of float type CoFe2O4/TiO2/ float bead composite photochemical catalyst and preparation method thereof | |
| CN103881662B (en) | Ternary nitric acid nano-molten salt heat transfer and storage medium, preparation method and application thereof | |
| CN102126762B (en) | Method for preparing NiO nano flowerlike microspheres with surface topography controllable | |
| CN103877971A (en) | Efficient visible-light-induced photocatalyst and preparation method thereof | |
| CN103911121A (en) | Nanometer molten binary nitrate heat-transfer heat-storage medium and preparation method thereof | |
| CN105694820B (en) | A kind of preparation method of hydrated salt-metal organic framework composite phase-change material | |
| CN103599737A (en) | Magnetic nano material with carbon shell layer and preparation method thereof | |
| CN103586048A (en) | Nano-Pd magnetic catalyst, its preparation method, and its use in liquid phase catalysis reaction | |
| CN105600828A (en) | Preparation method of porous nano CuFe2O4 | |
| CN106824272B (en) | A kind of nuclear grade ion-exchange resins based composites and preparation method thereof | |
| CN104353495A (en) | Preparation method and application of multiple magnetic mesoporous catalysts | |
| CN111203256A (en) | SnS2/Au/g-C3N4Preparation method and application of composite photocatalyst | |
| Liu et al. | Preparation and characterization of novel CuS/SiO2@ n‐octadecane phase‐change nanocapsules enhanced photothermal conversion for solar energy utilization | |
| CN104888853A (en) | Graphene supported PVP stable nanometer Ru catalyst, preparation method and uses thereof | |
| CN105385965B (en) | Method for preparing CoB amorphous alloy based on ZIF-67 framework material | |
| CN103586049A (en) | Bimetallic magnetic catalyst and its preparation method and use in Heck reaction | |
| CN105688967A (en) | Bismuth tungstate/boron nitride composite photocatalytic material and preparation method thereof | |
| CN109273289A (en) | Solvent method prepares Ni-based cobalt acid magnesium base composite material and its application | |
| CN105498776A (en) | Nickel ferrite composite photocatalytic material and preparation method thereof | |
| CN101480616A (en) | Catalyst for synthesizing methanol by fluidized bed and preparation method thereof | |
| CN103055867B (en) | Nickel catalyst and preparation method and application thereof | |
| CN109054758B (en) | Preparation method of high-temperature phase change heat storage material with core-shell structure | |
| CN116371447A (en) | double-Z heterojunction photocatalyst and preparation method and application thereof | |
| CN102407120B (en) | Preparation method of Cu/p-NiO/n-NiFe2O4 composite semiconductor photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140903 Termination date: 20161108 |