CN114130391B - Preparation method of iron-based carbon-aluminum composite material and application of iron-based carbon-aluminum composite material in catalytic reforming of biomass tar - Google Patents
Preparation method of iron-based carbon-aluminum composite material and application of iron-based carbon-aluminum composite material in catalytic reforming of biomass tar Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 44
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000002028 Biomass Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000001833 catalytic reforming Methods 0.000 title claims abstract description 8
- 238000003723 Smelting Methods 0.000 claims abstract description 48
- 239000002699 waste material Substances 0.000 claims abstract description 47
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 31
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002916 wood waste Substances 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 150000007524 organic acids Chemical class 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000001764 infiltration Methods 0.000 claims abstract description 5
- 230000008595 infiltration Effects 0.000 claims abstract description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims 1
- 239000002893 slag Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 239000007789 gas Substances 0.000 description 17
- 241000219000 Populus Species 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002023 wood Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000007233 catalytic pyrolysis Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
- C10J3/60—Processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2200/00—Details of gasification apparatus
- C10J2200/06—Catalysts as integral part of gasifiers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Processing Of Solid Wastes (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of an iron-based carbon-aluminum composite material and application of the iron-based carbon-aluminum composite material in catalytic reforming of biomass tar, wherein the preparation method comprises the steps of removing impurities on the surface of aluminum smelting waste residue; carrying out hot infiltration pretreatment on the aluminum smelting waste residue in organic acid, continuously stirring, filtering and drying to obtain activated powdery aluminum smelting waste residue, baking, and cooling to room temperature; adding the baked powdery aluminum smelting waste residue into a ferric nitrate solution, performing ultrasonic dispersion, and baking the aluminum smelting waste residue loaded with iron to obtain an aluminum-iron material; and uniformly mixing the crushed wood waste with the aluminum-iron material, roasting, cooling and taking out to obtain the iron-based carbon-aluminum composite material. The iron-loaded carbon-aluminum composite material is prepared by using the byproduct aluminum-smelting waste slag in the aluminum-smelting industry and cheap and easily-obtained wood waste as main raw materials, and the preparation method is convenient and rapid and has low energy consumption.
Description
Technical Field
The invention belongs to the technical field of biomass energy utilization, and particularly relates to a preparation method of an iron-based carbon-aluminum composite material and application of the iron-based carbon-aluminum composite material in catalytic reforming of biomass tar.
Background
With the increasing consumption of non-renewable resources and the increasing serious environmental problems, biomass energy is a hot spot of extensive research by virtue of its characteristics of small harm to the environment, abundant sources, convenient storage and transportation, low cost and price. Through the pyrolysis and gasification technology, the biomass can be converted into pyrolysis gas, biochar and tar, so that the resource utilization of the biomass is effectively realized. However, in the biomass pyrolysis process, the problems of low combustible gas content, pipeline blockage caused by tar, energy loss and the like exist. However, the catalytic cracking method can effectively remove tar and improve the yield of combustible gas by selecting a proper catalyst. As a byproduct of aluminum smelting industry, aluminum smelting waste slag is rich in Al2O3The alloy also contains active components such as Ga, Mg, K, Si and the like, and also contains heavy metals such as Cr, Cu, Zn and the like, so that the alloy has resource property and pollution property, and is easy to cause heavy metal pollution if the alloy is not properly treated.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
One of the purposes of the invention is to provide a preparation method of an iron-based carbon-aluminum composite material, which is characterized in that aluminum-smelting waste residues and wood waste are utilized to prepare a catalyst for preparing synthesis gas by catalytic reforming of biomass tar, and iron is added into the aluminum-smelting waste residues as an active component, so that the resource utilization of the aluminum-smelting waste residues can be realized, the hydrogen production and carbon monoxide of the biomass tar can be promoted, the resource utilization rate is improved, and the purification and high-value utilization of the biomass tar are effectively promoted.
In order to solve the technical problems, the invention provides the following technical scheme: a method for preparing an iron-based carbon-aluminum composite material comprises the following steps,
removing impurities on the surface of the aluminum smelting waste residue;
carrying out hot infiltration pretreatment on the aluminum smelting waste residue in organic acid, continuously stirring, filtering and drying to obtain activated powdery aluminum smelting waste residue, baking, and cooling to room temperature;
adding the baked powdery aluminum smelting waste residue into a ferric nitrate solution, performing ultrasonic dispersion, and baking the aluminum smelting waste residue loaded with iron to obtain an aluminum-iron material;
and uniformly mixing the crushed wood waste with the aluminum-iron material, roasting, cooling and taking out to obtain the iron-based carbon-aluminum composite material.
As a preferable embodiment of the method for preparing the iron-based carbon-aluminum composite material of the present invention, wherein: and removing impurities on the surface of the aluminum smelting waste residue, and roasting the aluminum smelting waste residue for 2-4 hours at 500-700 ℃.
As a preferable embodiment of the method for producing an iron-based carbon-aluminum composite material of the present invention, wherein: the concentration of the organic acid is 0.5-2 mol/L, and the mass ratio of the organic acid to the aluminum-smelting waste residue is 1: 1-4.
As a preferable embodiment of the method for producing an iron-based carbon-aluminum composite material of the present invention, wherein: and carrying out thermal permeation pretreatment at the temperature of 150-200 ℃.
As a preferable embodiment of the method for producing an iron-based carbon-aluminum composite material of the present invention, wherein: and baking at the temperature of 500-600 ℃.
As a preferable embodiment of the method for producing an iron-based carbon-aluminum composite material of the present invention, wherein: the baked powdery aluminum-smelting waste slag is added into a ferric nitrate solution according to the mass ratio of Fe to Al of 0.5-2: 100.
As a preferable embodiment of the method for producing an iron-based carbon-aluminum composite material of the present invention, wherein: the crushed wood waste and the aluminum-iron material are uniformly mixed, and the mass ratio of the wood waste to the aluminum-iron material is 0.5-3: 1.
As a preferable embodiment of the method for producing an iron-based carbon-aluminum composite material of the present invention, wherein: and roasting at the roasting temperature of 600-800 ℃ for 1-2 h.
Another object of the present invention is to provide an iron-based carbon-aluminum composite material obtained by the above-mentioned preparation method.
Another object of the present invention is to provide the use of the iron-based carbon-aluminum composite material as described above in catalytic reforming of biomass tar.
Compared with the prior art, the invention has the following beneficial effects:
the iron-loaded carbon-aluminum composite material is prepared by using the byproduct aluminum-smelting waste slag in the aluminum-smelting industry and cheap and easily-obtained wood waste as main raw materials, and the preparation method is convenient and rapid and has low energy consumption.
According to the invention, the iron-loaded carbon-aluminum composite material is used as a catalyst to pyrolyze the biomass, so that the yield of the synthetic gas can be obviously improved, the yield of the synthetic gas can be improved by more than 60%, the yield of tar can be effectively reduced, the yield of liquid is controlled to be below 10%, heavy components in the tar are greatly reduced, and the industrial process of the pyrolysis process is effectively promoted.
The invention fully utilizes industrial waste, improves the components of the pyrolysis gas by a catalytic cracking method, realizes resource utilization of the aluminum smelting waste slag, and relieves the problem of energy waste to a certain extent.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive labor. Wherein:
FIG. 1 is a schematic view of the structure of the pyrolysis experimental apparatus of the present invention.
Fig. 2 is a schematic structural diagram of a nitrogen protection device in embodiment 3 of the present invention.
Fig. 3 is a schematic view of the blocking member completely blocking the feeding port in embodiment 3 of the present invention.
Fig. 4 is a schematic view of the feed core of embodiment 3 of the present invention when it is separated from the discharge hole.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying the present invention are described in detail below with reference to examples.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein, and it will be appreciated by those skilled in the art that the present invention may be practiced without departing from the spirit and scope of the present invention and that the present invention is not limited by the specific embodiments disclosed below.
Furthermore, the references herein to "one embodiment" or "an embodiment" refer to a particular feature, structure, or characteristic that may be included in at least one implementation of the present invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
(1) Roasting the aluminum smelting waste residue at 600 ℃ for 3 hours to remove impurities on the surface of the aluminum smelting waste residue;
(2) and (3) mixing the roasted aluminum smelting waste residue with 1mol/L acetic acid according to the weight ratio of 1:1, performing hot infiltration pretreatment at 150 ℃, continuously stirring at the stirring speed of 150r/min, filtering and drying to obtain activated powdery aluminum smelting waste residue, baking at the high temperature of 550 ℃, and cooling to room temperature for later use;
(3) pouring aluminum-smelting waste residue powder into a ferric nitrate solution by adopting an excess impregnation method according to the proportion of Fe/Al being 1:100, placing the mixture into an ultrasonic generator, wherein the ultrasonic frequency is 90W, so that iron ions are fully dispersed into the aluminum-smelting waste residue, and placing the aluminum-smelting waste residue loaded with iron into a high-temperature furnace at 550 ℃ for baking for 4 hours to obtain an aluminum-iron material;
(4) crushing poplar wood to be below 40 meshes, wherein the mass ratio of the crushed poplar wood to the crushed poplar wood is 1: and (3) uniformly mixing the mixture 1 and the aluminum-iron material obtained in the step (3), placing the mixture in a tube furnace, roasting the mixture for 1 hour at the temperature of 600 ℃ in the nitrogen atmosphere, cooling and taking out the mixture to obtain the iron-based carbon-aluminum composite material.
The physical parameters of the obtained iron-based carbon-aluminum composite material were measured, and the results showed that the specific surface area was 509.8m2Per g, pore volume 0.52cm3(ii)/g, pore diameter is 4.1 nm.
Comparative example 1
(1) Roasting the aluminum smelting waste residue for 3 hours at the temperature of 600 ℃ to remove impurities on the surface of the aluminum smelting waste residue;
(2) and (3) adding the roasted aluminum-smelting waste residue into 1mol/L acetic acid according to the proportion of 1: 1, performing hot infiltration pretreatment at 150 ℃, continuously stirring at the stirring speed of 150r/min, filtering and drying to obtain activated powdery aluminum smelting waste residue, baking at the high temperature of 550 ℃, and cooling to room temperature for later use;
(3) crushing poplar wood to be below 40 meshes, wherein the mass ratio of the crushed poplar wood to the crushed poplar wood is 1: 1 and (3) uniformly mixing the aluminum-smelting waste residues baked in the step (2), placing the mixture in a tube furnace, roasting the mixture for 1 hour at the temperature of 600 ℃ in the nitrogen atmosphere, cooling and taking out the mixture to obtain the carbon-aluminum composite material.
The physical parameters of the obtained carbon-aluminum composite material were measured, and the results showed that the specific surface area was 286.6m2/g。
Example 2
The iron-based carbon-aluminum composite materials prepared in example 1 and comparative example 1 were used as catalysts to perform pyrolysis experiments on biomass, and the structure diagram of the pyrolysis experimental equipment is shown in fig. 1. It mainly includes first section pyrolysis oven 100 and second section pyrolysis oven 200 of connection in proper order, and first section pyrolysis oven 100 and second section pyrolysis oven 200 are by temperature controller 300 control furnace temperature, and first section pyrolysis oven 100 and second section pyrolysis oven 200 still are connected with nitrogen gas jar 500, provide N by nitrogen gas jar 500 2Atmosphere; and a condenser 400 into which products pyrolyzed by the first-stage pyrolysis furnace 100 and the second-stage pyrolysis furnace 200 enter and from which pyrolysis gas is discharged; the condenser 400 includes a first-stage condenser 401, a second-stage condenser 402, and a third-stage condenser 403 connected in series.
Specifically, the material is put into the first stage pyrolysis furnace 100, the catalyst is placed in the second stage pyrolysis furnace 200, the nitrogen gas is supplied into the first stage pyrolysis furnace 100 and the second stage pyrolysis furnace 200 through the nitrogen gas tank 500, and the gas flow rate is controlled by the rotameter 501. The temperature in the first-stage pyrolysis furnace 100 and the second-stage pyrolysis furnace 200 is controlled by the temperature controller 300 to perform catalytic pyrolysis, the pyrolysis product sequentially passes through a first-stage condenser 401, a second-stage condenser 402 and a third-stage condenser 403, liquid and gas products are collected, and the yield of each product is measured.
Poplar was placed in the first stage pyrolysis furnace, the carbon-aluminum composite material prepared in comparative example 1 was placed in the second stage pyrolysis furnace with nitrogen as a shielding gas and a carrier gas flow rate of 90 ml/min. Activating the catalyst at 800 ℃ for 40min, and then carrying out catalytic pyrolysis on the biomass at 200-900 ℃ to obtain a liquid product, pyrolysis gas and semicoke, wherein the yield is 26%, 52% and 22%, the yield of hydrogen is 148ml/g, the yield of carbon monoxide is 143ml/g, the yield of methane is 77ml/g, and the yield of carbon dioxide is 79 ml/g.
Poplar was placed in a first stage pyrolysis furnace, the iron-based carbon-aluminum composite material prepared in example 1 was used as a catalyst and placed in a second stage pyrolysis furnace, nitrogen was used as a shielding gas, and the flow rate of the carrier gas was 90 ml/min. Activating the catalyst at 800 ℃ for 40min, and then carrying out catalytic pyrolysis on the biomass at 200-900 ℃ to obtain a liquid product, pyrolysis gas and semicoke, wherein the yield is 19%, 60% and 21%, the yield of hydrogen is 152ml/g, the yield of carbon monoxide is 148ml/g, the yield of methane is 68ml/g, and the yield of carbon dioxide is 95 ml/g.
As a blank control example, poplar is crushed to below 40 meshes and added into a first-stage pyrolysis furnace, pyrolysis is carried out at 200-900 ℃, and a pyrolysis liquid product, pyrolysis gas and pyrolysis semicoke are obtained, wherein the yield is 43%, 34% and 23%, the yield of hydrogen is 42ml/g, the yield of carbon monoxide is 44ml/g, the yield of methane is 16ml/g, and the yield of carbon dioxide is 48 ml/g.
Example 3
In the test process of example 2, it is found that a large amount of air enters the pyrolysis furnace along with the poplar during the feeding process, so that a large amount of oxygen exists in the pyrolysis furnace, oxidation reaction at high temperature is easily caused, and the cracking efficiency is reduced.
Therefore, in order to further improve the cracking efficiency, in this embodiment 3, a nitrogen protection device 600 is added to the pyrolysis experimental equipment in embodiment 2, and the nitrogen protection device 600 is installed at the feed port 101 of the first stage pyrolysis furnace 100, as shown in fig. 2;
The nitrogen protection device 600 comprises a cavity 601, a plugging piece 602 and a discharging core 603, poplar wood enters from a feeding port 601a on the side wall of the cavity 601, the plugging piece 602 is controlled by a pneumatic control component 603 to move, the plugging piece 602 can completely plug the feeding port 601a, the discharging core 603 is controlled by a control component 604 to move, and the discharging core 603 can completely plug a discharging port 601 b;
the pneumatic control assembly 603 comprises a pneumatic control shell 603a and a pneumatic control plug 603b, the pneumatic control plug 603b divides the inner cavity of the pneumatic control shell 603a into a pneumatic control cavity 603c and an exhaust cavity 603d which are mutually independent in the pneumatic control shell 603a, wherein the pneumatic control cavity 603c is provided with an air inlet 603c-1, the air inlet 603c-1 is connected with the nitrogen tank 500, the exhaust cavity 603d is provided with an exhaust hole 603d-1, the plugging piece 602 is connected with the pneumatic control plug 603b through a guide rod 603e, the plugging piece 602 is positioned below the material inlet 601a, and N pneumatic control cavity 603c is filled with N through the nitrogen tank 5002The pneumatic control plug 603b drives the plugging member 602 to move until the feeding port 601a is completely plugged by the plugging member 602, so as to achieve the purpose of preventing external air from entering, as shown in fig. 3. It should be noted that, the inner top of the pneumatic control housing 603a has a stopper, and when the pneumatic control plug 603b moves upward to contact the stopper, the blocking piece 602 just completely blocks the feeding port 601 a.
The control assembly 604 comprises a piston 604a and a spring 604b, the piston 604a is arranged in the cavity 601, the piston 604a divides the cavity 601 into a material cavity 601c and an auxiliary cavity 601d which are independent from each other, wherein the material inlet 601a is arranged on the side wall of the material cavity 601c, the guide rod 603e penetrates through the piston 604a, and the guide rod 603e is arranged in a sealing and sliding manner with the piston 604a through a sliding seal ring; the material cavity 601c is provided with an air inlet 601c-1, the air inlet 601c-1 is connected with the nitrogen tank 500, the auxiliary cavity 601d is provided with a perforation 601d-1, the discharging core 603 is connected with the piston 604a through a connecting rod 604c, the inner top of the auxiliary cavity 601d is provided with a guide groove, the connecting rod 604c penetrates through the piston 604a and goes deep into the guide groove to move in a guiding way, the spring 604b is connected between the piston 604a and the inner top of the auxiliary cavity 601d, and the connecting rod 604c is fixedly connected with the piston 604 a; n is filled into the material cavity 601c through the nitrogen tank 5002Piston, piston604a drives the discharging core 603 to move until the discharging core 603 is separated from the discharging hole 601b, so as to achieve the purpose that the material in the material cavity 601c enters the feeding hole 101 of the first stage pyrolysis furnace 100, as shown in fig. 4.
Wherein the volume of the material cavity 601c is larger than that of the pneumatic control cavity 603c, and the nitrogen tank 500 simultaneously fills N into the pneumatic control cavity 603c and the material cavity 601c 2Firstly, the air control plug 603b is pushed to move to drive the plugging piece 602 to move until the material inlet 601a is completely plugged by the plugging piece 602, and at this time, the material cavity 601c is in a relatively sealed state, and the material cavity 601c is in a state of being accompanied by N in the material cavity 601c2Gradually increasing, pressure increases gradually, promotes piston 604a and removes, drives out the material core 603 and removes until the material core 603 breaks away from discharge gate 601b, and the material in the material chamber 601c gets into the feed inlet 101 of first section pyrolysis furnace 100, and in this process, the oxygen content greatly reduced in the material chamber 601c avoids the oxidation reaction under the high temperature, can improve the schizolysis efficiency.
By adopting the same pyrolysis test as example 2, the same pyrolysis experimental equipment as example 3 and the iron-based carbon-aluminum composite material prepared in example 1 as the catalyst, the pyrolysis liquid product, pyrolysis gas and pyrolysis semicoke are finally obtained, and the yield is 16%, 65% and 19% respectively; it can be seen that the cracking efficiency is increased, in line with the theoretical value.
The method treats the aluminum smelting waste residue and the biomass at high temperature, can take the waste biomass as a carbon source to be fused and solidified with heavy metals in the aluminum smelting waste residue, reduces heavy metal pollution, simultaneously can convert the biomass on the aluminum smelting waste residue into hydrogen through the action of active metals, can absorb and mineralize carbon dioxide with mineral substances in the aluminum smelting waste residue, reduces the emission of the carbon dioxide, and prepares the carbon-aluminum composite material to play the role of Al component 2O3The physical skeleton characteristics and the catalytic function advantages of the carbon and the active metal components are applied to the synthesis gas preparation by the catalytic reforming of the biomass tar.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (8)
1. A preparation method of an iron-based carbon-aluminum composite material is characterized by comprising the following steps: comprises the steps of (a) preparing a substrate,
removing impurities on the surface of the aluminum smelting waste residue;
carrying out hot infiltration pretreatment on the aluminum smelting waste residue in organic acid, continuously stirring, filtering and drying to obtain activated powdery aluminum smelting waste residue, baking, and cooling to room temperature;
adding the baked powdery aluminum-smelting waste residues into a ferric nitrate solution according to the mass ratio of Fe to Al of 0.5-2: 100, performing ultrasonic dispersion, and baking the aluminum-smelting waste residues loaded with iron to obtain an aluminum-iron material;
uniformly mixing the crushed wood waste with the aluminum-iron material, wherein the mass ratio of the wood waste to the aluminum-iron material is 0.5-3: 1, roasting, cooling and taking out to obtain the iron-based carbon-aluminum composite material.
2. The method for preparing an iron-based carbon-aluminum composite material according to claim 1, wherein: and removing impurities on the surface of the aluminum smelting waste residue, and roasting the aluminum smelting waste residue at 500-700 ℃ for 2-4 h.
3. The method for producing an iron-based carbon-aluminum composite material according to claim 1 or 2, characterized in that: the concentration of the organic acid is 0.5-2 mol/L, and the mass ratio of the organic acid to the aluminum-smelting waste residue is 1: 1-4.
4. The method for producing an iron-based carbon-aluminum composite material according to claim 3, characterized in that: and carrying out thermal permeation pretreatment at the temperature of 150-200 ℃.
5. The method for producing an iron-based carbon-aluminum composite material according to any one of claims 1, 2 and 4, wherein: and baking at the temperature of 500-600 ℃.
6. The method for producing an iron-based carbon-aluminum composite material according to claim 1, characterized in that: and roasting at the roasting temperature of 600-800 ℃ for 1-2 h.
7. The iron-based carbon-aluminum composite material obtained by the production method according to any one of claims 1 to 6.
8. Use of the iron-based carbon-aluminum composite material of claim 7 in catalytic reforming of biomass tar.
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