CN113731419B - Application and preparation of oxygen carrier in chemical looping hydrogen production - Google Patents
Application and preparation of oxygen carrier in chemical looping hydrogen production Download PDFInfo
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- CN113731419B CN113731419B CN202111143794.3A CN202111143794A CN113731419B CN 113731419 B CN113731419 B CN 113731419B CN 202111143794 A CN202111143794 A CN 202111143794A CN 113731419 B CN113731419 B CN 113731419B
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000001301 oxygen Substances 0.000 title claims abstract description 142
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 142
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 73
- 239000001257 hydrogen Substances 0.000 title claims abstract description 72
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 67
- 239000000126 substance Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229960000892 attapulgite Drugs 0.000 claims abstract description 69
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 69
- 239000000203 mixture Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000446 fuel Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 238000006722 reduction reaction Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 37
- 230000000694 effects Effects 0.000 abstract description 6
- 238000009841 combustion method Methods 0.000 abstract description 2
- 238000007654 immersion Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 59
- 229910052742 iron Inorganic materials 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
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- 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
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Abstract
The invention belongs to the technical field of chemical looping hydrogen production, and discloses an application of an oxygen carrier in chemical looping hydrogen production and a preparation method thereof. The oxygen carrier is made of attapulgite and Fe 2 O 3 The composition is that the attapulgite is used as a carrier and Fe 2 O 3 Is loaded on a carrier. According to the mass percentage, fe in the oxygen carrier 2 O 3 The content of (A) is 40-80%, and the content of the attapulgite is 20-60%. The preparation method of the oxygen carrier adopts an immersion combustion method. In the chemical looping hydrogen production process, the reaction temperature of the prepared oxygen carrier in fuel is 750-950 ℃, the reaction temperature in water vapor is 750-950 ℃, and the reaction temperature in oxygen is 750-950 ℃. The oxygen carrier has high reaction activity, high hydrogen production amount, good stability and simple preparation method in the chemical looping hydrogen production, and is suitable for industrial application.
Description
Technical Field
The invention belongs to the field of chemical looping hydrogen production, and particularly relates to application of an oxygen carrier in chemical looping hydrogen production and a preparation method thereof.
Background
With the rapid rise of global energy demand and the increasing emission of greenhouse gases, hydrogen energy (H) 2 ) Is receiving great attention as a clean energy carrier. Steam reforming of methane (SMR) is currently the leading technology for large-scale hydrogen production in industry. However, this process not only consumes a lot of energy, but also results in a lot of CO 2 Emission, and global warming is increased. Therefore, the development of a high-efficiency, low-energy-consumption and low-CO catalyst is urgently needed 2 A novel hydrogen production technology for emission.
Chemical looping hydrogen production (CLH), which combines chemical looping combustion with steam-iron hydrogen production, is a promising hydrogen production technology. Typically, the oxygen carrier is circulated between a Fuel Reactor (FR), a Steam Reactor (SR) and an Air Reactor (AR), with oxygen transfer occurring during the CLH process. Oxygen carrier for oxidation of carbonaceous fuels to CO in FR 2 And H 2 O, then reacts with water vapor in SR to generate hydrogen, and finally is completely oxidized and regenerated in AR to complete the cycle. In this way, the CLH process can achieve high purity hydrogen production and inherent CO 2 And (4) separating.
The oxygen carrier in CLH needs to have good conversion of steam to hydrogen in SRCapability. At present, the main research is the metallic oxide oxygen carrier such as Fe, ni, co, mn, cd, etc. Through research and screening, fe 2 O 3 Is considered to be an ideal oxygen carrier material in the CLH process. However, fe 2 O 3 Poor reduction kinetics are exhibited during high temperature operation. Therefore, in order to increase the reactivity of the oxygen carrier and enhance the stability, it is generally carried on a carrier (Al) having a higher talman temperature 2 O 3 、MgAl 2 O 4 、TiO 2 、ZrO 2 ) To improve mechanical and chemical properties. However, these support materials are generally obtained by chemical synthesis, which inevitably increases the production cost of the oxygen carrier material.
The preparation method of the oxygen carrier mainly comprises a solid phase method, a gas phase method and a liquid phase method. The solid phase method is simple to operate, but the particle size of the generated particles is difficult to control; the gas phase method has large equipment investment, high preparation cost, complex operation and lower yield; the sol-gel method and the dipping method which are commonly used in the liquid phase method have some defects, the sol-gel method can cause incomplete complexation in the complexation process, the dispersion degree of oxygen carrier metals prepared by the traditional dipping method is low, the uniformity of dipping loading is not enough, and the effective exertion of the catalytic performance of active components is influenced.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention aims to provide the application and the preparation of the oxygen carrier in the chemical looping hydrogen production.
Based on the purpose, the invention adopts the following technical scheme:
the invention provides an application of an oxygen carrier in chemical looping hydrogen production, wherein the oxygen carrier is prepared from attapulgite and Fe 2 O 3 The composition is that the attapulgite is used as a carrier and Fe 2 O 3 Is loaded on a carrier.
Preferably, the oxygen carrier contains Fe by mass percent 2 O 3 The content of (A) is 40% -80%, and the content of the attapulgite is 20% -60%.
More preferably, the oxygen carrier is powder, and the particle size range is 60-80 meshes.
Preferably, the preparation method of the oxygen carrier comprises the following steps:
(1) Dissolving ferric salt in water to obtain a negative carrier liquid, adding attapulgite powder into the negative carrier liquid, and uniformly dispersing to obtain a mixture;
(2) And (2) evaporating the mixture prepared in the step (1) to dryness to obtain a mixture, and finally calcining and grinding the mixture to obtain the oxygen carrier powder.
More preferably, the iron salt is Fe (NO) 3 ) 3 ·9H 2 O。
Preferably, the calcining temperature in the step (2) is 700-900 ℃, and the calcining time is 3-5 h.
Preferably, the particle size range of the attapulgite powder is 80 to 100 meshes.
Preferably, the attapulgite powder is a commercial product or a powder obtained by washing, drying and grinding attapulgite; the specific operation steps of the washing process are as follows: standing and soaking the attapulgite for 24 hours at room temperature by using deionized water, and filtering out upper-layer impurities; the drying temperature is 105-120 ℃, and the drying time is 8-12 h.
Preferably, the dispersion method in the step (1) is ultrasonic treatment, the ultrasonic treatment power is 80-100W, and the treatment time is 2-3 h.
Preferably, the specific process of the evaporation process in step (2) is as follows: firstly, stirring the mixture in a water bath at the temperature of 80-90 ℃ for 8-10 h; then drying treatment is carried out, the drying temperature is 100-120 ℃, and the drying time is 10-24 h.
Preferably, in the operation process of preparing hydrogen by a chemical looping, fuel and the oxygen carrier are added into a reactor, and reduction reaction is carried out at 750-950 ℃; after the reduction reaction is finished, the oxygen carrier and the water vapor react at the temperature of 750-950 ℃; then oxygen is introduced to keep the temperature unchanged, and oxidation is continued to complete the whole chemical-looping hydrogen production process.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the invention, fe 2 O 3 The loaded attapulgite is applied to the chemical looping hydrogen production as an oxygen carrier, so that the reaction activity can be improved, and the hydrogen yield can be increased. In one of the examples, it can be seen that Fe 2 O 3 /Al 2 O 3 H of oxygen carrier after 10 times of circulation 2 The average yield was 6.3 mL, the average CO conversion was 91%, and the oxygen carrier samples prepared according to the invention were H under the same conditions 2 The average value of the yield can reach 9.4 mL, the average value of the CO conversion rate is 95%, and the hydrogen yield is obviously improved.
(2) The attapulgite is directly used as a carrier, because the attapulgite is a natural water-containing magnesium-rich aluminosilicate clay mineral with a chain lamellar structure, has larger specific surface area, rich pore canals and good thermal stability, does not need to undergo chemical reaction for synthesis, can shorten the preparation process flow, improves the production efficiency and reduces the production cost.
(3) The invention adopts a dipping combustion method to mix Fe 2 O 3 Loaded on attapulgite, and has less reaction steps and less three wastes compared with a liquid phase reduction method. And an ultrasonic field is introduced in the preparation process of the oxygen carrier, the cavitation of ultrasonic waves plays a role in shearing aggregates, agglomeration and growth among colloidal particles are prevented, the preparation of nano powder is facilitated, substances are uniformly mixed in the dipping process, the uneven local concentration is eliminated, the reaction speed is increased, and new phase generation is stimulated.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail by the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail with reference to examples.
1. Preparation of oxygen carriers
Example 1
An oxygen carrier applied to chemical-looping hydrogen production comprises 60% of Fe by mass percentage 2 O 3 And 40% of attapulgite, wherein the attapulgite is used as a carrier, and Fe 2 O 3 Is loaded on a carrier.
A preparation method of an oxygen carrier applied to chemical looping hydrogen production comprises the following steps:
(1) Taking 100 g of agricultural attapulgite, standing and soaking the agricultural attapulgite for 24 hours at room temperature by using deionized water, filtering out upper-layer impurities, placing the agricultural attapulgite in a drying oven at 120 ℃ for drying for 12 hours, smashing the agricultural attapulgite by using a stirrer, and sieving the agricultural attapulgite by using a 100-mesh sieve to obtain attapulgite powder.
(2) 15.15 g Fe (NO) are weighed out 3 ) 3 ·9H 2 Dissolving O in a proper amount of deionized water to form a negative carrier liquid, then adding 2.00 g of the attapulgite powder into the negative carrier liquid to obtain a mixture, placing the mixture in an ultrasonic generator, carrying out ultrasonic treatment for 2 hours under the power of 100W, and dispersing uniformly to obtain a dispersion liquid.
(3) Heating and stirring the dispersion liquid in water bath at 85 ℃ by adopting a magnetic stirrer for 8 hours, and simultaneously evaporating water; then placing the mixture in a blast drying oven, and drying the mixture for 10 hours at 120 ℃; and after drying is finished, a mixture is obtained, the mixture is calcined in a muffle furnace at 900 ℃ for 3 h, and the calcined sample is ground.
Example 2
An oxygen carrier applied to chemical-looping hydrogen production comprises 60% of Fe by mass percentage 2 O 3 And 40% of attapulgite, wherein the attapulgite is used as a carrier and Fe 2 O 3 Is loaded on a carrier.
The preparation method of the oxygen carrier applied to chemical looping hydrogen production is basically the same as that of the embodiment 1, and the difference is that: and (4) in the step (3), calcining the mixture in a muffle furnace at 800 ℃.
Example 3
An oxygen carrier applied to chemical-looping hydrogen production comprises 60% of Fe by mass percentage 2 O 3 And 40 percent of attapulgite clay,wherein, the attapulgite is used as a carrier, and Fe 2 O 3 Is loaded on a carrier.
The preparation method of the oxygen carrier applied to chemical looping hydrogen production is basically the same as that of the embodiment 1, and the difference is that: and (4) calcining the mixture in a muffle furnace at 700 ℃.
Example 4
An oxygen carrier applied to chemical-looping hydrogen production comprises 80% of Fe by mass percentage 2 O 3 And 20% of attapulgite, wherein the attapulgite is used as a carrier, and Fe 2 O 3 Is loaded on a carrier.
The preparation method of the oxygen carrier applied to chemical looping hydrogen production is basically the same as that of the embodiment 1, and the difference is that: in the step (2), 20.20 g of Fe (NO) is added 3 ) 3 ·9H 2 Dissolving O in a certain amount of deionized water to form a negative carrier liquid, and then adding 1.00 g of attapulgite powder into the negative carrier liquid to obtain a mixture; and (4) in the step (3), calcining the mixture in a muffle furnace at 800 ℃.
Example 5
An oxygen carrier applied to chemical-looping hydrogen production comprises 50% of Fe by mass percentage 2 O 3 And 50% of attapulgite, wherein the attapulgite is used as a carrier, and Fe 2 O 3 Is loaded on a carrier.
The preparation method of the oxygen carrier applied to chemical looping hydrogen production is basically the same as that of the embodiment 1, and the difference is that: in the step (2), 12.625 g of Fe (NO) is added 3 ) 3 ·9H 2 Dissolving O in a certain amount of deionized water to form a negative carrier liquid, and then adding 2.50 g of attapulgite powder into the negative carrier liquid to obtain a mixture; in the step (3), the mixture is calcined in a muffle furnace at 800 ℃.
Example 6
An oxygen carrier applied to chemical-looping hydrogen production comprises 80% of Fe by mass percentage 2 O 3 And 20% of attapulgite, wherein the attapulgite is a carrier,Fe 2 O 3 is loaded on a carrier.
The preparation method of the oxygen carrier applied to chemical looping hydrogen production is basically the same as that of the embodiment 1, and the difference is that: and (2) placing the attapulgite washed by the water in the step (1) in a drying oven at 105 ℃ for drying for 8 hours, smashing by using a stirrer, and sieving by using a 80-mesh sieve.
Example 7
An oxygen carrier applied to chemical looping hydrogen production comprises 40% of Fe by mass percentage 2 O 3 And 60% of attapulgite, wherein the attapulgite is used as a carrier, and Fe 2 O 3 Is loaded on a carrier.
The preparation method of the oxygen carrier applied to chemical looping hydrogen production is basically the same as that of the embodiment 1, and the difference is that: and (3) carrying out ultrasonic treatment for 3 h at the power of 80W in the step (2).
Example 8
An oxygen carrier applied to chemical-looping hydrogen production comprises 50% of Fe by mass percentage 2 O 3 And 50% of attapulgite, wherein the attapulgite is used as a carrier, and Fe 2 O 3 Is loaded on a carrier.
The preparation method of the oxygen carrier applied to chemical looping hydrogen production is basically the same as that of the embodiment 1, and the difference is that: in the step (2), ultrasonic treatment is carried out for 2.5 h under the power of 90W.
Example 9
An oxygen carrier applied to chemical-looping hydrogen production comprises 60% of Fe by mass percentage 2 O 3 And 40% of attapulgite, wherein the attapulgite is used as a carrier, and Fe 2 O 3 Is loaded on a carrier.
The preparation method of the oxygen carrier applied to chemical looping hydrogen production is basically the same as that of the embodiment 1, and the difference is that: and (4) in the step (3), heating and stirring the dispersion liquid in a water bath at 80 ℃ for 10 hours.
Example 10
Applied to chemical-looping hydrogen productionOxygen carrier, wherein the oxygen carrier consists of 80 percent of Fe by mass percentage 2 O 3 And 20% of attapulgite, wherein the attapulgite is used as a carrier, and Fe 2 O 3 Is loaded on a carrier.
The preparation method of the oxygen carrier applied to chemical looping hydrogen production is basically the same as that of the embodiment 1, and the difference is that: and (3) heating and stirring the dispersion liquid in water bath at 90 ℃ for 9 h.
Example 11
An oxygen carrier applied to chemical-looping hydrogen production comprises 50% of Fe by mass percentage 2 O 3 And 50% of attapulgite, wherein the attapulgite is used as a carrier, and Fe 2 O 3 Is loaded on a carrier.
The preparation method of the oxygen carrier applied to chemical looping hydrogen production is basically the same as that of the embodiment 1, and the difference is that: and (3) drying in an air drying oven at 100 ℃ for 24 h.
Example 12
An oxygen carrier applied to chemical looping hydrogen production comprises 40% of Fe by mass percentage 2 O 3 And 60% of attapulgite, wherein the attapulgite is used as a carrier, and Fe 2 O 3 Is loaded on a carrier.
The preparation method of the oxygen carrier applied to chemical looping hydrogen production is basically the same as that of the embodiment 1, and the difference is that: and (3) drying in an air drying oven at the temperature of 110 ℃ for 18 h.
Example 13
An oxygen carrier applied to chemical looping hydrogen production comprises 40% of Fe by mass percentage 2 O 3 And 60% of attapulgite, wherein the attapulgite is used as a carrier, and Fe 2 O 3 Is loaded on a carrier.
The preparation method of the oxygen carrier applied to chemical looping hydrogen production is basically the same as that of the embodiment 1, and the difference is that: and (3) calcining the mixture in a muffle furnace at 700 ℃ for 5 h.
Example 14
An oxygen carrier applied to chemical looping hydrogen production comprises 40% of Fe by mass percentage 2 O 3 And 60% of attapulgite, wherein the attapulgite is used as a carrier, and Fe 2 O 3 Is loaded on a carrier.
The preparation method of the oxygen carrier applied to chemical looping hydrogen production is basically the same as that of the embodiment 1, and the difference is that: in the step (3), the mixture is calcined in a muffle furnace at 800 ℃ for 4 h.
Comparative example 1
Fe applied to chemical-looping hydrogen production 2 O 3 /Al 2 O 3 Oxygen carrier, wherein the oxygen carrier consists of 60% of Fe by mass percentage 2 O 3 And 40% of Al 2 O 3 And (4) forming.
Fe applied to chemical-looping hydrogen production 2 O 3 /Al 2 O 3 The preparation method of the oxygen carrier is basically the same as that of the embodiment 1, and the difference is that: 2.00 g of Al is added in step (1) 2 O 3 The attapulgite powder is replaced and added into the negative carrier liquid to obtain a mixture.
And (3) testing the performance of the oxygen carrier:
(I) oxygen carrier reaction performance test
And (3) evaluating the reaction performance of the prepared oxygen carrier by adopting a fixed bed reactor, wherein the oxygen carrier is 0.5g, the reaction temperature is 850 ℃, and the reaction pressure is normal pressure. The test process comprises three processes of complete oxidation, reduction and hydrogen production: introducing O in the complete oxidation stage 2 The flow rate is 60 mL/min, the reaction temperature is 850 ℃, the reaction pressure is normal pressure, and the reaction time is 10 min; introducing N in the reduction stage 2 And CO, N 2 The flow is 40 mL/min, the CO flow is 20 mL/min, the temperature is kept at 850 ℃, and the reaction time is 20 min; n is introduced in the hydrogen production stage 2 And H 2 O，N 2 The flow rate is 40 mL/min, H 2 The O flow is 0.05 mL/min, the temperature is kept at 850 ℃, and the reaction time is 10 min. N is introduced after each stage 2 And fully purging the gas in the pipe.
（1）Fe 2 O 3 Influence of the mass ratio to the support on the reactivity of the oxygen carrier
To investigate Fe 2 O 3 The inventors have conducted experiments on the influence of the mass ratio of the carrier on the reaction performance of the oxygen carrier, i.e., examples 2, 4, and 5, respectively, on the corresponding Fe 2 O 3 The mass ratio of the attapulgite carrier to the attapulgite carrier is respectively as follows: 3: 2, 4: 1, 1: 1. And (3) evaluating the reaction performance of the prepared oxygen carrier by adopting a fixed bed reactor, wherein the test process is as shown in the steps, and calculating the average value after circulating for 10 times. The results of the performance evaluation are shown in Table 1.
TABLE 1 Fe 2 O 3 Influence of the ratio of mass to carrier on the reactivity of oxygen carriers
As can be seen from Table 1, when Fe 2 O 3 When the content of the oxygen carrier is reduced, the CO conversion rate and H of the iron-based oxygen carrier when the attapulgite prepared by the invention is used as a carrier 2 The yield shows the trend of rising first and falling second, and H is obtained after 10 cycles 2 The average yield of (2) can reach 12.0 mL.
(2) Effect of calcination temperature on oxygen carrier reactivity
In order to investigate the influence of the calcination temperature on the oxygen carrier reactivity, the inventors carried out the following experiments, namely example 1, example 2, example 3 and comparative example 1, respectively, and the calcination temperatures were: 900. 800 deg.C, 700 deg.C and 900 deg.C. And (3) evaluating the reaction performance of the prepared oxygen carrier by adopting a fixed bed reactor, wherein the test process is as shown in the steps, and calculating the average value after circulating for 10 times. The results of the performance evaluation are shown in Table 2.
TABLE 2 Effect of calcination temperature on oxygen carrier reactivity
As can be seen from Table 2, the conversion of CO and H of the iron-based oxygen carrier when the attapulgite prepared by the present invention is used as a carrier when the calcination temperature is isothermally decreased 2 The yield showed a tendency of rising first and then falling. However, under the same calcination temperature condition, the iron-based oxygen carrier is higher than Fe when the attapulgite prepared by the invention is used as a carrier 2 O 3 /Al 2 O 3 CO conversion and H of oxygen carrier 2 The yield is improved, and higher reaction activity is shown, wherein H 2 The yield is obviously improved.
(II) oxygen carrier BET characterization test
To further investigate the influence of the calcination temperature on the oxygen carrier characterization, the inventors performed the following experiments, i.e., example 1, example 2, example 3, and comparative example 1, respectively, and the calcination temperatures were: 900. 800 deg.C, 700 deg.C and 900 deg.C. The BET surface area, the pore volume and the average pore diameter of the oxygen carrier are characterized and tested by a nitrogen adsorption/desorption method, and each oxygen carrier sample is degassed at 200 ℃ for 3 hours and then measured at-196 ℃ before formal measurement. The results are shown in Table 3.
TABLE 3 Effect of calcination temperature on oxygen carrier characterization
As can be seen from table 3, when the calcination temperature is lowered isothermally, the BET surface area and pore volume of the iron-based oxygen carrier when the attapulgite prepared by the present invention is used as a carrier both show an increasing tendency, and the average pore diameter shows a decreasing tendency. And the BET surface area ratio Fe of the iron-based oxygen carrier when the attapulgite is used as the carrier under the same conditions 2 O 3 /Al 2 O 3 The oxygen carrier is large, and the increase of the BET surface area of the oxygen carrier is supposed to promote the reaction performance of the oxygen carrier to be enhanced by combining the test result of the reaction performance of the oxygen carrier.
2. Application of oxygen carrier
Example 15
A method for chemical looping hydrogen production by using an oxygen carrier specifically comprises the following steps: adding fuel and an oxygen carrier into a reactor, and carrying out reduction reaction at 750 ℃; after the reduction reaction is finished, reacting the oxygen carrier with water vapor at 750 ℃; then introducing oxygen to keep the temperature unchanged, and continuing to oxidize to complete the whole chemical-looping hydrogen production process. Wherein the oxygen carrier is the oxygen carrier prepared in example 2.
Example 16
The content of a method for producing hydrogen by utilizing an oxygen carrier through chemical looping is basically the same as that of the embodiment 15, and the difference is that: the reaction temperature of the oxygen carrier in fuel is 800 ℃, the reaction temperature of the oxygen carrier in water vapor is 800 ℃, and the reaction temperature of the oxygen carrier in oxygen is 800 ℃. Wherein the oxygen carrier is the oxygen carrier prepared in example 2.
Example 17
The content of a method for producing hydrogen by utilizing an oxygen carrier through chemical looping is basically the same as that of the embodiment 15, and the difference is that: the reaction temperature of the oxygen carrier in fuel is 850 ℃, the reaction temperature of the oxygen carrier in water vapor is 850 ℃, and the reaction temperature of the oxygen carrier in oxygen is 850 ℃. Wherein the oxygen carrier is the oxygen carrier prepared in example 2.
Example 18
The content of a method for producing hydrogen by utilizing an oxygen carrier through a chemical looping is basically the same as that of the embodiment 15, and the difference is that: the reaction temperature of the oxygen carrier in fuel is 900 ℃, the reaction temperature of the oxygen carrier in water vapor is 900 ℃, and the reaction temperature of the oxygen carrier in oxygen is 900 ℃. Wherein the oxygen carrier is the oxygen carrier prepared in example 2.
Example 19
The content of a method for producing hydrogen by utilizing an oxygen carrier through chemical looping is basically the same as that of the embodiment 15, and the difference is that: the reaction temperature of the oxygen carrier in fuel is 950 ℃, the reaction temperature in water vapor is 950 ℃ and the reaction temperature in oxygen is 950 ℃. Wherein the oxygen carrier is the oxygen carrier prepared in example 2.
In conclusion, the present invention effectively overcomes the disadvantages of the prior art and has high industrial utilization value. The above-described embodiments are intended to illustrate the substance of the present invention, but are not intended to limit the scope of the present invention. It will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the true spirit and scope of the invention.
Claims (7)
1. The application of the oxygen carrier in chemical looping hydrogen production is characterized in that the oxygen carrier is prepared from attapulgite and Fe 2 O 3 The composition is that the attapulgite is used as a carrier and Fe 2 O 3 Loaded on a carrier; according to the mass percentage, the oxygen carrier contains Fe 2 O 3 The content of the attapulgite is 40 to 80 percent, and the content of the attapulgite is 20 to 60 percent;
the preparation method of the oxygen carrier comprises the following steps: (1) Dissolving ferric salt in water to obtain a negative carrier liquid, adding attapulgite powder into the negative carrier liquid, and uniformly dispersing to obtain a mixture; (2) Evaporating the mixture prepared in the step (1) to obtain a mixture, and finally calcining and grinding the mixture to obtain the oxygen carrier powder; the calcination temperature is 800 ℃.
2. The application of the oxygen carrier in chemical looping hydrogen production according to claim 1, wherein the calcination time in the step (2) is 3-5 h.
3. The application of the oxygen carrier in the chemical looping hydrogen production according to claim 2, wherein the particle size range of the attapulgite powder is 80-100 meshes.
4. The application of the oxygen carrier in the chemical looping hydrogen production according to claim 3, wherein the attapulgite powder is obtained by washing, drying and grinding attapulgite.
5. The application of the oxygen carrier in chemical looping hydrogen production according to claim 4, wherein the dispersion mode in the step (1) is ultrasonic treatment, the ultrasonic treatment power is 80-100W, and the treatment time is 2-3 h.
6. The application of the oxygen carrier in chemical looping hydrogen production according to claim 5, wherein the specific process of the drying-to-dryness treatment in the step (2) is as follows: firstly, stirring at 80-90 ℃ for 8-10 h; then drying treatment is carried out, the drying temperature is 100-120 ℃, and the drying time is 10-24 h.
7. The application of the oxygen carrier according to any one of claims 1 to 6 in chemical looping hydrogen production, wherein the specific operation of using the oxygen carrier to produce hydrogen by chemical looping is as follows: adding fuel and oxygen carrier into a reactor, and carrying out reduction reaction at 750-950 ℃; after the reduction reaction is finished, the oxygen carrier and the water vapor react at the temperature of 750-950 ℃; then oxygen is introduced to keep the temperature unchanged, and oxidation is continued to complete the whole chemical-looping hydrogen production process.
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