CN104986730A - Preparation method for copper slag oxygen carrier used for chemical looping hydrogen production - Google Patents
Preparation method for copper slag oxygen carrier used for chemical looping hydrogen production Download PDFInfo
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- CN104986730A CN104986730A CN201510331929.7A CN201510331929A CN104986730A CN 104986730 A CN104986730 A CN 104986730A CN 201510331929 A CN201510331929 A CN 201510331929A CN 104986730 A CN104986730 A CN 104986730A
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- copper ashes
- oxygen carrier
- hydrogen production
- preparation
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000010949 copper Substances 0.000 title claims abstract description 77
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 77
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000001301 oxygen Substances 0.000 title claims abstract description 54
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 54
- 239000001257 hydrogen Substances 0.000 title claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000000126 substance Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002893 slag Substances 0.000 title abstract 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000004480 active ingredient Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims description 70
- 239000002956 ash Substances 0.000 claims description 70
- 239000000203 mixture Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 238000007493 shaping process Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910002607 Gd0.1Ce0.9O1.95 Inorganic materials 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000446 fuel Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UPLPHRJJTCUQAY-WIRWPRASSA-N 2,3-thioepoxy madol Chemical compound C([C@@H]1CC2)[C@@H]3S[C@@H]3C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@](C)(O)[C@@]2(C)CC1 UPLPHRJJTCUQAY-WIRWPRASSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017771 LaFeO Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a preparation method for a copper slag oxygen carrier used for chemical looping hydrogen production, and belongs to the technical field of energy catalysis. According to the preparation method, copper slag is dried, a modifying agent is added, and calcining treatment is conducted; a carrier, auxiliaries and active ingredients are added, and conventional forming is conducted according to requirements; finally, roasting is conducted, and the oxygen carrier used for the chemical looping hydrogen production is obtained. According to the method, resource utilization of the copper slag can be effectively achieved; the copper slag serves as a raw material to prepare the oxygen carrier used for the chemical looping hydrogen production, the preparation cost of the oxygen carrier can be obviously lowered, the cheap and available raw material is provided for scale production of the oxygen carrier, and a foundation is established for implement of a chemical looping hydrogen production technology; the chemical looping hydrogen production technology is combined with resourcilization of the copper slag, resources are efficiently utilized, use ratios of the resources and energy are improved, and technological support is provided for preparation and separation of pure hydrogen.
Description
Technical field
The present invention relates to a kind of preparation method of hydrogen production of chemical chain copper ashes base oxygen carrier, belong to energy catalysis technical field.
Technical background
Along with the mankind consume the quick growth of the energy, in human being's production, life, havoc environment and ecology balance has been used in a large number based on the carbon containing fossil energy of oil, coal, Sweet natural gas, the many Ecological and environmental problems caused, as " Greenhouse effect ", " PM2.5 " etc.CO
2be that the Greenhouse effect caused have been regarded as third generation air pollutant, PM2.5 is considered to the arch-criminal of haze weather.These problems have more and more received the concern of people, and " Copenhagen climate change conference " that be intended to discuss Global Green House Gas Emissions Reduction and low-carbon economy is subject to national governments and shows great attention to; " two Conferences " conservation culture at home from " 18 is large " to this year and environment protection become national focus especially.
The energy is the major issue that human kind sustainable development faces.The mankind just turn to current based on the liquid fuel epoch of oil, hydro carbons etc. from the past to the exploitation of the energy gradually based on the solid fuel epoch of timber, coal, and the current forward of development trend changes based on the direction of the geseous fuel such as methane, hydrogen.
In fuel gas, Hydrogen Energy is a kind of desirable fuel and energy carrier, there is the advantages such as aboundresources, recyclability, environment-friendly high-efficiency, that in all fossil oils, chemical fuel and the biofuel except nuclear fuel, calorific value is the highest, therefore, the development of Hydrogen Energy not only can meet the needs of environmental resources and Sustainable Socioeconomic Development, and brings the great change of world energy sources structure.The new forms of energy that Hydrogen Energy is faced adverse conditions as solution current mankind are just becoming the object studied energetically various countries.
As the secondary energy that future is important, the huge development & application of man power and material to Hydrogen Energy of all a large amount of input in countries in the world is studied.Along with the fast development of modern industry, Hydrogen Energy also becomes more and more extensive in the application of every field, and Hydrogen Energy demand is also growing.Under the situation that particularly energy and environment problem is increasingly severe, the arrival promoting hydrogen economy has particularly important effect for Sustainable Socioeconomic Development.Cheap, the efficient hydrogen producing technology of exploitation can solve the source of hydrogen economy, and accelerates the arrival of hydrogen economy.Current, China " 863 " and " 973 " in the works all using Hydrogen Energy as priority research areas, this has fully demonstrated the strategic position of Hydrogen Energy in energy development.
Hydrogen production of chemical chain (CLH) technology adopts water of decomposition circulation hydrogen production process in the oxidation step set up based on chemical chain (CL) and burning chemistry chains (CLC) technology.The ultimate principle of CLH technology utilizes traditional raw material and water vapor to carry out two gas-solid circulating reactions by means of the effect of oxygen carrier, and in reduction step, fuel and oxygen carrier react and lose lattice oxygen (M
xo
y+ δ CH
4→ M
xo
y-δ+ δ (2H
2+ CO)), water vapor and oxygen carrier reacting recovery lattice oxygen in oxidation step, produce pure hydrogen (M through condensation simultaneously
xo
y-δ+ δ H
2o → M
xo
y+ δ H
2).With the oxide compound (Fe of iron
3o
4) be the hydrogen production of chemical chain oxygen carrier of chief active species, due to the reactivity worth that it is superior, be considered to a kind of oxygen carrier having very much industrial prospect.But realize the industrial applications of Fe base oxygen carrier, the technology must finding a kind of cheapness realizes the mass-producing preparation of oxygen carrier.
China is the copper utilization of resources and output big country, thus the annual copper ashes producing more than 800 ten thousand tons nearly, in its copper ashes iron level be its XRD spectra of 38 ~ 42wt %(as shown in Figure 1).This part copper ashes can not well utilize, and still the one of resource is not wasted, and will take a large amount of soils, also pollutes ecotope simultaneously.
Summary of the invention
For above-mentioned Problems existing and deficiency, the present invention proposes a kind of preparation method utilizing hydrogen production of chemical chain copper ashes base oxygen carrier, realizes a large amount of utilizations of copper ashes, avoids and take a large amount of soil, cause the pollution of ecotope.
The present invention is realized by following technical proposal, specifically comprises the following steps:
(1) by copper ashes at temperature 110 ~ 300 DEG C dry 3 ~ 24 hours, to slough moisture in copper ashes and gaseous impurities; Being crushed to after granularity is 20 ~ 40 orders, adding properties-correcting agent, and under air or oxygen-enriched atmosphere, carrying out 800 ~ 1000 DEG C of high-temperature roastings 4 ~ 30 hours;
(2) add carrier, auxiliary agent and active ingredient in the copper ashes of gained in step (1) and mix, it is shaping then to carry out routine; The roasting at 800 ~ 1000 DEG C of mixture after shaping obtains copper ashes base oxygen carrier for 4 ~ 12 hours.
The copper ashes base oxygen carrier of step (2) gained is placed in CLH evaluating apparatus, carries out hydrogen manufacturing performance detection (its principle as shown in Figure 2).
Properties-correcting agent in described step (1) is one or more in MgO, BaO, CaO, adds properties-correcting agent by 30 ~ 50% of dry rear copper ashes quality; Properties-correcting agent be mainly used in follow-up roasting process with SiO
2in conjunction with and isolate and SiO
2ferriferous oxide, finally make the oxide compound of at high temperature these iron to be oxidizing to high oxide.
Carrier in described step (2) is one or more of indifferent oxide, as: SiO
2, TiO
2, Al
2o
3, be that 0 ~ 5:1 adds carrier by the mass ratio of copper ashes after carrier and drying.
Auxiliary agent in described step (2) is NaOH, KOH, K
2cO
3, Na
2cO
3in one or more, the addition of auxiliary agent be dry after copper ashes and carrier total mass 0 ~ 6%.
The active ingredient of described step (2) is NiO, CeO
2, Fe
2o
3, CuO, wustite, hexa-aluminate (as: BaFeAl
11o
19, LaFeAl
11o
19, LaNiAl
11o
19), uhligite (as: La system La
xca
1-xfeO
3-δwith Ba system BaFe
yzr
1-yo
3-δdeng) and Gd
0.1ce
0.9o
1.95in one or more, be that 0 ~ 2:1 adds active ingredient by the mass ratio of active ingredient and copper ashes oxide compound.
The routine of described step (2) is shaping is need to make powder, granular, coccoid or carry out global formation to mixture, as compressing tablet slabbing film, tubular film etc. according to use.
The purity of the carrier of described interpolation, auxiliary agent and active ingredient all will reach technical pure or analytical pure.
The present invention also has the following advantages:
(1) achieve recycling industry being produced to copper ashes, avoid a large amount of copper ashes to stack the drawback brought;
(2) copper ashes is that CLH oxygen carrier prepared by raw material, can be good at the preparation cost reducing oxygen carrier, for oxygen carrier mass-producing preparation provides a kind of raw material cheap and easy to get, simultaneously again for the enforcement of CLH technology is laid a good foundation;
(3) CLH technology is combined with the recycling of copper ashes, achieve turning waste into wealth of waste, improve the utilization ratio of natural resources and energy resources, for the preparation of pure hydrogen provides technical support with being separated;
Present method proposes a kind of method utilizing copper ashes preparative chemistry chain hydrogen manufacturing oxygen carrier, has far-reaching influence to the recycling of copper ashes and CLH technology.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of copper ashes;
Fig. 2 is the schematic diagram of CLH technology.
Embodiment
Illustrate content of the present invention further below in conjunction with embodiment, but these examples do not limit the scope of the invention.
Embodiment 1
The composition of the present embodiment copper ashes used
The method of copper ashes preparative chemistry chain hydrogen manufacturing oxygen carrier described in the present embodiment, specifically comprises the following steps:
(1) by copper ashes at temperature 300 DEG C dry 4 hours, to deviate from moisture; Being crushed to after granularity is 20 orders, getting the dried copper ashes of 1kg, adding the properties-correcting agent CaO of 0.3kg, and under the atmosphere of air, carry out calcining 30 hours with 800 DEG C;
(2) in the dried copper ashes of gained in step (1), add the carrier A l of 5kg
2o
3, the auxiliary agent NaOH of 0.01kg, and mix, then grind to form fine powder body, at then fine powder body is placed in 800 DEG C, roasting 12 hours, namely obtains CLH oxygen carrier.
(3) take the CLH oxygen carrier 1g of gained in step (2), use it for CLH evaluating apparatus, its average hydrogen output is: 200Ncm
3.
Embodiment 2
The composition of the present embodiment copper ashes used
The method of copper ashes preparative chemistry chain hydrogen manufacturing oxygen carrier described in the present embodiment, specifically comprises the following steps:
(1) by copper ashes at temperature 250 DEG C dry 8 hours, to deviate from moisture; Being crushed to after granularity is 30 orders, getting the dried copper ashes of 1kg, adding the properties-correcting agent CaO of 0.5kg, and under the atmosphere of air, carry out calcining 20 hours with 850 DEG C;
(2) in the dried copper ashes of gained in step (1), add the carrier (TiO of 2kg of 4kg
2with the SiO of 2kg
2), the 0.03kg auxiliary agent (Na of NaOH and the 0.02kg of 0.01kg
2cO
3), be that 2:1 adds and mixes by active ingredient NiO with the mass ratio of copper ashes oxide compound; Mixture makes the particulate state that granularity is 5mm; The roasting 10 hours at 850 DEG C of particle after shaping, namely obtains CLH oxygen carrier.
(3) take the CLH oxygen carrier 1g of gained in step (2), use it for CLH evaluating apparatus, its average hydrogen output is: 250Ncm
3.
Embodiment 3
The composition of the present embodiment copper ashes used
The method of copper ashes preparative chemistry chain hydrogen manufacturing oxygen carrier described in the present embodiment, specifically comprises the following steps:
(1) by copper ashes at temperature 200 DEG C dry 12 hours, to deviate from moisture; Being crushed to after granularity is 40 orders, getting the dried copper ashes of 1kg, adding the properties-correcting agent (CaO of BaO and 0.15kg of 0.15kg) of 0.3kg, and under oxygen-enriched atmosphere, carry out calcining 16 hours with 900 DEG C;
(2) in the dried copper ashes of gained in step (1), add the carrier (SiO of 1.5kg of 3kg
2with the Al of 1.5kg
2o
3), the auxiliary agent (K of KOH and the 0.01kg of 0.02kg of 0.03kg
2cO
3), by active constituent (Fe
2o
3, NiO and CeO
2mix in the ratio of 1:1:1) be that 1.5:1 adds with the mass ratio of copper ashes oxide compound, and mix; Mixture is made coccoid; The roasting 10 hours at 900 DEG C of bead after shaping, namely obtains CLH oxygen carrier.
(3) take the CLH oxygen carrier 1g of gained in step (2), use it for CLH evaluating apparatus, its average hydrogen output is: 285Ncm
3.
Embodiment 4
The composition of the present embodiment copper ashes used
The method of copper ashes preparative chemistry chain hydrogen manufacturing oxygen carrier described in the present embodiment, specifically comprises the following steps:
(1) by copper ashes at temperature 180 DEG C dry 16 hours, to deviate from moisture; Being crushed to after granularity is 40 orders, getting the dried copper ashes of 1kg, adding the properties-correcting agent (CaO of MgO and 0.25kg of 0.25kg) of 0.5kg, and under oxygen-enriched atmosphere, carry out calcining 12 hours with 950 DEG C;
(2) in the dried copper ashes of gained in step (1), add the carrier (SiO of 0.5kg of 2kg
2, 0.5kg Al
2o
3with the TiO of 1kg
2), by active constituent (CeO
2, NiO and LaFeO
3mix in the ratio of 1:2:3) be that 1:1 adds with the mass ratio of copper ashes oxide compound, and mix; Mixture carries out global formation; The roasting 8 hours at 950 DEG C of mixture after shaping, namely obtains CLH oxygen carrier.
(3) take the CLH oxygen carrier 1g of gained in step (2), use it for CLH evaluating apparatus, its average hydrogen output is: 270Ncm
3.
Embodiment 5
The composition of the present embodiment copper ashes used
The method of copper ashes preparative chemistry chain hydrogen manufacturing oxygen carrier described in the present embodiment, specifically comprises the following steps:
(1) by copper ashes at temperature 150 DEG C dry 20 hours, to deviate from moisture; Being crushed to after granularity is 40 orders, getting the dried copper ashes of 1kg, adding the properties-correcting agent (CaO of BaO and 0.1kg of MgO, 0.1kg of 0.1kg) of 0.3kg, and under oxygen-enriched atmosphere, carry out calcining 8 hours with 1000 DEG C;
(2) in the dried copper ashes of gained in step (1), add the carrier (SiO of 1kg of 2kg
2with the TiO of 1kg
2), the auxiliary agent (Na of NaOH, 0.02kg of 0.02kg of 0.06kg
2cO
3with the KOH of 0.02kg), by active constituent (La
0.7ca
0.3feO
3-δ, LaFeAl
11o
19with BaFe
0.8zr
0.2o
3-δmix in the ratio of 1:1:1) be that 0.8:1 adds with the mass ratio of copper ashes oxide compound, and mix, mixture is carried out compressing tablet slabbing film; By the roasting 6 hours at 1000 DEG C of the mixture after shaping, namely obtain the membranaceous oxygen carrier of CLH.
(3) take the CLH oxygen carrier 1g of gained in step (2), use it for CLH evaluating apparatus, its average hydrogen output is: 314Ncm
3.
Embodiment 6
The composition of the present embodiment copper ashes used
The method of copper ashes preparative chemistry chain hydrogen manufacturing oxygen carrier described in the present embodiment, specifically comprises the following steps:
(1) by copper ashes at temperature 110 DEG C dry 24 hours, to deviate from moisture; Being crushed to after granularity is 40 orders, getting the dried copper ashes of 1kg, adding the properties-correcting agent (BaO and 0.1kgCaO of MgO, 0.2kg of 0.2kg) of 0.5kg, and under oxygen-enriched atmosphere, carry out calcining 6 hours with 1000 DEG C;
(2) in the dried copper ashes of gained in step (1), add the carrier TiO of 1kg
2, the auxiliary agent (K of NaOH, 0.01kg of 0.01kg of 0.03kg
2cO
3with the KOH of 0.01kg), by active constituent (La
0.7ca
0.3feO
3-δ, BaFe
0.8zr
0.2o
3-δ, BaFeAl
11o
19with Gd
0.1ce
0.9o
1.95mix in the ratio of 1:2:3) be that 0.6:1 adds with the mass ratio of copper ashes oxide compound, and mix; Mixture is carried out compressing tablet slabbing film; By the roasting 6 hours at 1000 DEG C of the mixture after shaping, namely obtain the membranaceous oxygen carrier of CLH.
(3) take the CLH oxygen carrier 1g of gained in step (2), use it for CLH evaluating apparatus, its average hydrogen output is: 305Ncm
3.
Claims (5)
1. a hydrogen production of chemical chain preparation method for copper ashes base oxygen carrier, is characterized in that, specifically comprise the following steps:
(1) by copper ashes at temperature is 110 ~ 300 DEG C dry 3 ~ 24 hours, being then crushed to granularity is 20 ~ 40 orders, adds properties-correcting agent, and high-temperature roasting 4 ~ 30 hours under air or oxygen-enriched atmosphere, wherein calcining temperature is 800 ~ 1000 DEG C;
(2) add carrier, auxiliary agent and active ingredient in the copper ashes of gained in step (1) and mix, it is shaping then to carry out routine; The roasting at 800 ~ 1000 DEG C of mixture after shaping obtains copper ashes base oxygen carrier for 4 ~ 12 hours.
2. the preparation method of hydrogen production of chemical chain copper ashes base oxygen carrier according to claim 1, is characterized in that: the properties-correcting agent in described step (1) is one or more in MgO, BaO, CaO, adds properties-correcting agent by 30 ~ 50% of dry rear copper ashes quality.
3. the preparation method of hydrogen production of chemical chain copper ashes base oxygen carrier according to claim 1, is characterized in that: the carrier in described step (2) is SiO
2, TiO
2, Al
2o
3in one or more, be that 0 ~ 5:1 adds carrier by the mass ratio of copper ashes after carrier and drying.
4. the preparation method of hydrogen production of chemical chain copper ashes base oxygen carrier according to claim 1, is characterized in that: the auxiliary agent in described step (2) is NaOH, KOH, K
2cO
3, Na
2cO
3in one or more, the addition of auxiliary agent be dry after copper ashes and carrier total mass 0 ~ 6%.
5. the preparation method of hydrogen production of chemical chain copper ashes base oxygen carrier according to claim 1, is characterized in that: the active ingredient of described step (2) is NiO, CeO
2, Fe
2o
3, CuO, wustite, hexa-aluminate, uhligite and Gd
0.1ce
0.9o
1.95in one or more, be that 0 ~ 2:1 adds active ingredient by the mass ratio of active ingredient and copper ashes oxide compound.
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|---|---|---|---|
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|---|---|---|---|
| CN201510331929.7A CN104986730A (en) | 2015-06-16 | 2015-06-16 | Preparation method for copper slag oxygen carrier used for chemical looping hydrogen production |
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|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111732990A (en) * | 2020-06-22 | 2020-10-02 | 青岛理工大学 | Preparation process and method of oxygen carrier for chemical chain gasification of carbon-containing solid waste |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102410530A (en) * | 2011-10-26 | 2012-04-11 | 昆明理工大学 | Method for preparing oxygen carrier for chemical-looping combustion by utilizing copper residues |
| CN103274361A (en) * | 2013-05-28 | 2013-09-04 | 东北大学 | Oxygen-hydrogen co-production device and method based on chemical chain reaction |
-
2015
- 2015-06-16 CN CN201510331929.7A patent/CN104986730A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102410530A (en) * | 2011-10-26 | 2012-04-11 | 昆明理工大学 | Method for preparing oxygen carrier for chemical-looping combustion by utilizing copper residues |
| CN103274361A (en) * | 2013-05-28 | 2013-09-04 | 东北大学 | Oxygen-hydrogen co-production device and method based on chemical chain reaction |
Non-Patent Citations (1)
| Title |
|---|
| 曹湘洪: "《现代化工•冶金•材料•能源——中国工程院化工、冶金与材料工程学部第九届学术会议论文集》", 30 September 2012, 徐州：中国矿业大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111732990A (en) * | 2020-06-22 | 2020-10-02 | 青岛理工大学 | Preparation process and method of oxygen carrier for chemical chain gasification of carbon-containing solid waste |
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Application publication date: 20151021 |