CN114534744A - Preparation method of solid acid catalyst based on aluminous ash-green carbon-based double-carrier - Google Patents
Preparation method of solid acid catalyst based on aluminous ash-green carbon-based double-carrier Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 75
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000011973 solid acid Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 42
- 239000002028 Biomass Substances 0.000 claims abstract description 30
- 238000003723 Smelting Methods 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002699 waste material Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 230000004913 activation Effects 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000005470 impregnation Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 240000008042 Zea mays Species 0.000 claims description 5
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 235000005822 corn Nutrition 0.000 claims description 5
- 239000010902 straw Substances 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 2
- 244000105624 Arachis hypogaea Species 0.000 claims description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 2
- 235000018262 Arachis monticola Nutrition 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 235000020232 peanut Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims 7
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000004411 aluminium Substances 0.000 abstract description 3
- 150000001398 aluminium Chemical class 0.000 abstract 1
- 239000002893 slag Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000197 pyrolysis Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- -1 Ethanol Acetic acid 1, 4-dioxane Chemical compound 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- 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
- B01J35/615—100-500 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/14—Injection, e.g. in a reactor or a fuel stream during fuel production
- C10L2290/141—Injection, e.g. in a reactor or a fuel stream during fuel production of additive or catalyst
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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
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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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
- 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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Abstract
The invention discloses a preparation method of a solid acid catalyst based on aluminium smelting slag-green carbon-based dual-carrier, which comprises the steps of carrying out activation treatment on aluminium smelting waste slag to prepare activated aluminium ash; heating the biomass to 300-400 ℃ in a nitrogen atmosphere, and carbonizing for 10-20 h to obtain a carbon-based matrix; uniformly mixing a carbon-based matrix with concentrated sulfuric acid, sulfonating at 100-300 ℃ for 3-6 h, cooling, washing with water, and drying to obtain a carbon-based precursor; uniformly mixing activated aluminum ash and a carbon-based precursor, adding 1, 4-dioxane, carrying out ultrasonic-assisted impregnation for 10-30 min, coprecipitating for 10-12 h, filtering, leaving residues, and drying at 105-120 ℃ to obtain a carbon-based material; and (3) placing the carbon-based material into a constant-temperature transverse tubular furnace, heating to 400-600 ℃ in a nitrogen atmosphere, and calcining for 2-3 hours at a constant temperature to obtain the aluminum smelting ash-green carbon-based double-carrier solid acid catalyst. The catalyst has high catalytic activity and stability, large specific surface area and wide pore canal structure.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a solid acid catalyst based on aluminum smelting ash-green carbon-based dual-carrier.
Background
With the increasing consumption of non-renewable energy sources such as coal, petroleum, natural gas, etc., research, development and utilization of renewable energy sources have become a focus of great attention. The biomass energy is favored by people by virtue of the characteristics of small harm to the environment, rich sources, convenient storage and transportation, low cost and price and the like. China has abundant raw material supply of biomass energy, can effectively solve the problems of current resource shortage, environmental pollution and the like if the biomass resources are developed and utilized to the maximum extent, and has important significance for realizing carbon peak-reaching carbon neutralization.
At present, the application technologies of biomass energy in China include a solidified fuel technology, a liquid fuel technology, a gas fuel technology, a power generation technology and the like.
However, most of these utilization techniques of biomass resources use various catalysts to promote the reaction process; therefore, one of the key points in the development of the biomass energy industry is to develop various catalysts to meet the processing requirements of different raw materials. Al (Al)2O3Because of the large specific surface area, the strong mechanical stability and the thermal stability, the catalyst is widely used for biomass pyrolysis gasification catalysts and carriers, and shows strong catalytic activity. Conventionally used Al2O3The catalyst is prepared from analytically pure reagents, and the reaction cost is increased to a certain extent.
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.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of a solid acid catalyst based on an aluminous ash-green carbon-based dual-carrier.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a solid acid catalyst based on aluminum smelting ash-green carbon-based dual-carrier comprises the following steps,
activating the aluminum smelting waste residues to prepare activated aluminum ash;
heating the biomass to 300-400 ℃ in a nitrogen atmosphere, and carbonizing for 10-20 h to obtain a carbon-based matrix;
uniformly mixing a carbon-based matrix with concentrated sulfuric acid, sulfonating at 100-300 ℃ for 3-6 h, cooling, washing with water, and drying to obtain a carbon-based precursor;
uniformly mixing activated aluminum ash and a carbon-based precursor, adding 1, 4-dioxane, carrying out ultrasonic-assisted impregnation for 10-30 min, coprecipitating for 10-12 h, filtering, leaving residues, and drying at 105-120 ℃ to obtain a carbon-based material;
and (3) placing the carbon-based material into a constant-temperature transverse tubular furnace, heating to 400-600 ℃ in a nitrogen atmosphere, and calcining for 2-3 hours at a constant temperature to obtain the aluminum smelting ash-green carbon-based double-carrier solid acid catalyst.
As a preferable scheme of the preparation method of the solid acid catalyst based on the aluminous ash-green carbon-based dual-carrier, the method comprises the following steps: the activation treatment of the aluminum smelting waste residue comprises the following steps,
by the concentration of 1, 3, 5, 7mol/LRemoving light ash on the surface of the aluminum-smelting waste residue by using medium-strong acid, and roasting at 550-600 ℃ to obtain the aluminum-smelting waste residue containing more than 99% of Al2O3The aluminum ash powder of (4);
and (2) carrying out auxiliary activation on the aluminum ash powder through 1-5 mol/L weak acid, then carrying out centrifugal separation at a rotating speed of 2000r/min, baking the aluminum ash powder at a constant temperature of 500-700 ℃ for 3-6 h in an air atmosphere, and naturally cooling the aluminum ash powder to room temperature to obtain activated aluminum ash.
As a preferable scheme of the preparation method of the solid acid catalyst based on the aluminous ash-green carbon-based dual-carrier, the method comprises the following steps: the medium strong acid includes sulfuric acid, nitric acid and phosphoric acid, and the weak acid includes acetic acid, hydrofluoric acid and phenol.
As a preferable scheme of the preparation method of the solid acid catalyst based on the aluminous ash-green carbon-based dual-carrier, the method comprises the following steps: the auxiliary activation comprises rotary evaporation, wherein the rotary evaporation time is 20-30 min.
As a preferable scheme of the preparation method of the solid acid catalyst based on the aluminous ash-green carbon-based dual-carrier, the method comprises the following steps: the biomass comprises corn straws, sawdust, rice hulls and peanut shells, and the particle size of the biomass is 10-20 microns.
As a preferable scheme of the preparation method of the solid acid catalyst based on the aluminous ash-green carbon-based dual-carrier, the method comprises the following steps: the carbon-based matrix and concentrated sulfuric acid are uniformly mixed, wherein the volume ratio of the carbon-based matrix to the concentrated sulfuric acid is 10: 1-3, and the mass fraction of the concentrated sulfuric acid is 80-90%.
As a preferable scheme of the preparation method of the solid acid catalyst based on the aluminous ash-green carbon-based dual-carrier, the method comprises the following steps: the activated aluminum ash and the carbon-based precursor are uniformly mixed, and then 1, 4-dioxane is added, wherein the mass ratio of the activated aluminum ash to the carbon-based precursor is 1: 1-2, and the sum of the mass of the 1, 4-dioxane, the activated aluminum ash and the carbon-based precursor is 4:10 in terms of the volume mass ratio g: mL.
As a preferable scheme of the preparation method of the solid acid catalyst based on the aluminous ash-green carbon-based dual-carrier, the method comprises the following steps: and carrying out ultrasonic assisted dipping for 10-30 min, wherein the ultrasonic power is 80W.
As a preferable scheme of the preparation method of the solid acid catalyst based on the aluminous ash-green carbon-based dual-carrier, the method comprises the following steps: and heating to 400-600 ℃ in a nitrogen atmosphere, wherein the heating rate is 20 ℃/min.
The invention further aims to overcome the defects in the prior art and provide a product prepared by the preparation method of the solid acid catalyst based on the aluminium smelting ash-green carbon-based dual-carrier, wherein the specific surface area of the product is 216-352m2The diameter of the pore channel is 10-15 nm.
The invention has the beneficial effects that:
(1) the invention provides a method for synthesizing a solid acid catalyst based on aluminum smelting ash and green carbon-based dual-carrier, in particular to a method for synthesizing a solid acid catalyst based on aluminum smelting ash and green carbon-based dual-carrier, which is used for directionally converting biomass tar into hydrogen-rich gas.
(2) The preparation process of the catalyst is carried out at lower temperature and normal pressure, so that the problem of unsafety caused by high temperature and high pressure is avoided; meanwhile, the directional selectivity and the ion exchange property of active ingredients of the aluminum smelting ash are carried out by adopting different auxiliary methods, so that the active groups in the aluminum smelting ash are ensured to be fully contacted with the carbon-based precursor during subsequent coprecipitation, and the catalyst shows higher catalytic activity and stability and larger specific surface area (216 ion 352 m)2(g) and a wide pore size (pore diameter of 10-15 nm).
(3) The catalyst of the invention has lower preparation cost and simple process.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a diagram of a catalyst prepared in example 2 of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the 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
The embodiment provides a preparation method of a solid acid catalyst based on aluminous ash-green carbon-based dual-carrier, which mainly comprises the following steps:
(1) removing light ash on the surface of the aluminum smelting waste residue by using 1mol/L sulfuric acid, and roasting at 600 ℃ to obtain aluminum ash powder;
carrying out rotary evaporation auxiliary activation on the obtained aluminum ash powder by using 1mol/L acetic acid;
and (3) carrying out centrifugal separation on the aluminum ash solution subjected to weak acid treatment at the rotating speed of 2000r/min, after complete exchange of metal ions is realized, baking the aluminum ash solution at the constant temperature of 500 ℃ for 3 hours in the air atmosphere, naturally cooling the aluminum ash solution to the room temperature, and storing the aluminum ash solution for later use.
(2) Heating the biomass corn straws to 300 ℃ in a nitrogen atmosphere (with the flow rate of 50ml/min), and carbonizing for 10 hours to obtain a carbon-based matrix;
uniformly mixing the obtained carbon-based matrix with concentrated sulfuric acid according to the mass-to-volume ratio of 10:1, sulfonating for 3 hours in a constant-temperature oil bath kettle at the temperature of 150 ℃, cooling, and washing with deionized water until no SO is contained in filtrate4 2-And drying at 105 ℃ to obtain the carbon-based precursor.
(3) Uniformly mixing activated aluminum ash and the obtained carbon-based precursor according to a ratio of 1:1, and then adding 1, 4-dioxane into the mixture according to a mass-volume ratio of 4: dissolving 10, fully stirring, carrying out ultrasonic-assisted impregnation for 10min under the power of 80W, carrying out coprecipitation for 12h, filtering by using a sand core funnel to obtain filtrate and residue, and reserving the residue for drying at the temperature of 105 ℃;
then placing the mixture in a constant-temperature transverse tube furnace, raising the temperature to 600 ℃ at the heating rate of 20 ℃/min in the nitrogen atmosphere, and calcining the mixture for 3 hours at the constant temperature to obtain the powder with the specific surface area of 216m2The alumina slag-green carbon-based dual-carrier solid acid catalyst has the pore diameter of 10 nm.
Example 2
The embodiment provides a preparation method of a solid acid catalyst based on aluminous ash-green carbon-based dual-carrier, which mainly comprises the following steps:
(1) removing light ash on the surface of the aluminum smelting waste residue by using 1mol/L sulfuric acid, and roasting at 600 ℃ to obtain aluminum ash powder; carrying out rotary evaporation auxiliary activation on the obtained aluminum ash powder by using 1mol/L acetic acid;
and (3) carrying out centrifugal separation on the aluminum ash solution subjected to weak acid treatment at the rotating speed of 2000r/min, after complete exchange of metal ions is realized, baking the aluminum ash solution at the constant temperature of 600 ℃ for 3 hours in the air atmosphere, naturally cooling the aluminum ash solution to the room temperature, and storing the aluminum ash solution for later use.
(2) Heating the biomass corn straws to 380 ℃ in a nitrogen atmosphere (with the flow rate of 50ml/min), and carbonizing for 10 hours to obtain a carbon-based matrix;
uniformly mixing the obtained carbon-based matrix with concentrated sulfuric acid according to the mass-to-volume ratio of 10:2, sulfonating for 3 hours in a constant-temperature oil bath kettle at the temperature of 150 ℃, cooling, and washing with deionized water until no SO is contained in filtrate4 2-And drying at 105 ℃ to obtain the carbon-based precursor.
(3) Uniformly mixing activated aluminum ash and the obtained carbon-based precursor according to a ratio of 1:1, and then adding 1, 4-dioxane into the mixture according to a mass-volume ratio of 4: dissolving 10, fully stirring, carrying out ultrasonic-assisted impregnation for 20min under the power of 80W, carrying out coprecipitation for 12h, filtering by using a sand core funnel to obtain filtrate and residue, and reserving the residue for drying at the temperature of 105 ℃;
then placing the mixture in a constant-temperature transverse tube furnace, raising the temperature to 600 ℃ at the heating rate of 20 ℃/min in the nitrogen atmosphere, and calcining the mixture for 3 hours at the constant temperature to obtain the material with the specific surface area of 352m2The alumina slag-green carbon-based dual-carrier solid acid catalyst has the pore diameter of 15 nm.
The prepared catalyst is shown in figure 1.
Example 3
The influence of the mass ratio of the activated aluminum ash to the obtained carbon-based precursor on the performance of the prepared catalyst was investigated under the conditions of example 2, and the other conditions were the same as example 2, and the conditions and results are shown in table 1.
TABLE 1
As can be seen from table 1, the optimal mixing ratio of the aluminum ash to the carbon-based precursor is 1:1, too much carbon-based material affects the mechanical strength of the catalyst, and too much aluminum ash affects the channel structure and specific surface area of the catalyst.
Example 4
The activated aluminum ash prepared in example 2 is applied to catalytic biomass tar pyrolysis, and the conversion rate is 70.5%;
heating the biomass corn straws to 380 ℃ in a nitrogen atmosphere (with the flow rate of 50ml/min), and carbonizing for 10 hours to obtain a carbon-based matrix; uniformly mixing the obtained carbon-based matrix with concentrated sulfuric acid according to the mass-to-volume ratio of 10:2, sulfonating for 3 hours in a constant-temperature oil bath kettle at the temperature of 150 ℃, cooling, and washing with deionized water until no SO is contained in filtrate4 2-At a temperature of 105 deg.CDrying at a certain temperature to obtain a carbon-based precursor, placing the carbon-based precursor in a constant-temperature transverse tubular furnace, raising the temperature to 600 ℃ at a heating rate of 20 ℃/min in a nitrogen atmosphere, and calcining at a constant temperature for 3 hours to obtain a biomass catalyst, wherein the biomass catalyst is applied to catalyzing pyrolysis of biomass tar, and the conversion rate of the biomass tar is 76.4%;
TABLE 2
| Activated aluminum ash | Biomass catalyst | |
| Catalytic biomass tar pyrolysis conversion (%) | 70.5 | 76.4 |
The biochar serving as a byproduct of biomass pyrolysis has a rich pore structure and a large specific surface area, can well adsorb light tar compounds, and has a good catalytic effect on the removal of biomass tar by serving as a catalyst carrier.
Example 5
The effect of different solvents on the catalyst was investigated under the conditions of example 2, and the other process conditions were the same as in example 2, and the results are shown in table 3.
TABLE 3
| Solvent(s) | Water (W) | Ethanol | Acetic acid | 1, 4-dioxane |
| Catalytic biomass tar pyrolysis conversion (%) | 85.2 | 86.7 | 92.9 | 98.1 |
It can be seen that the biomass carbon carrier and the aluminum smelting ash have good dispersibility in the 1, 4-dioxane, and can ensure the full contact of the active components and the carrier. Water, ethanol, acetic acid, etc. are also selected as solvents, and the dispersibility and solubility are not as good as those of 1, 4-dioxane.
Example 6
The effect of different alumina-smelting ash-green carbon-based dual-carrier solid acid catalyst calcination temperatures on the catalyst under the conditions of example 2 was investigated and the results are shown in table 4.
TABLE 4
| Calcination temperature | 400 | 500 | 600 | 800 |
| Catalytic biomass tar pyrolysis conversion (%) | 89.3 | 94.4 | 98.1 | 92.4 |
It can be seen that, compared with 400 and 500 ℃, after calcination at 600 ℃, the catalyst has higher mechanical strength, stronger bonding force of the two materials, optimal catalytic effect, and reduced performance due to overhigh temperature.
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 (10)
1. A preparation method of a solid acid catalyst based on aluminum smelting ash-green carbon-based dual-carrier is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
activating the aluminum smelting waste residue to prepare activated aluminum ash;
heating the biomass to 300-400 ℃ in a nitrogen atmosphere, and carbonizing for 10-20 h to obtain a carbon-based matrix;
uniformly mixing a carbon-based matrix with concentrated sulfuric acid, sulfonating at 100-300 ℃ for 3-6 h, cooling, washing with water, and drying to obtain a carbon-based precursor;
uniformly mixing activated aluminum ash and a carbon-based precursor, adding 1, 4-dioxane, carrying out ultrasonic-assisted impregnation for 10-30 min, coprecipitating for 10-12 h, filtering, leaving residues, and drying at 105-120 ℃ to obtain a carbon-based material;
and (3) placing the carbon-based material into a constant-temperature transverse tubular furnace, heating to 400-600 ℃ in a nitrogen atmosphere, and calcining for 2-3 hours at a constant temperature to obtain the aluminum smelting ash-green carbon-based double-carrier solid acid catalyst.
2. The method for preparing the solid acid catalyst based on the aluminous clinker-green carbon-based dual carrier as claimed in claim 1, wherein: the activation treatment of the aluminum smelting waste residue comprises the following steps,
removing light ash on the surface of the aluminum-smelting waste residue by using medium-strong acid with the concentration of 1, 3, 5 and 7mol/L in sequence, and roasting at 550-600 ℃ to obtain the aluminum-smelting waste residue containing more than 99% of Al2O3The aluminum ash powder of (4);
and (2) carrying out auxiliary activation on the aluminum ash powder through 1-5 mol/L weak acid, then carrying out centrifugal separation at a rotating speed of 2000r/min, baking the aluminum ash powder at a constant temperature of 500-700 ℃ for 3-6 h in an air atmosphere, and naturally cooling the aluminum ash powder to room temperature to obtain activated aluminum ash.
3. The method for preparing the solid acid catalyst based on the aluminous clinker-green carbon-based dual carrier as claimed in claim 2, wherein: the medium strong acid includes sulfuric acid, nitric acid and phosphoric acid, and the weak acid includes acetic acid, hydrofluoric acid and phenol.
4. The process for preparing an aluminous clinker-green carbon-based dual-carrier solid acid catalyst according to claim 2 or 3, wherein: the auxiliary activation comprises rotary evaporation, wherein the rotary evaporation time is 20-30 min.
5. The method for preparing the solid acid catalyst based on the aluminous clinker-green carbon-based dual carrier as claimed in claim 1, wherein: the biomass comprises corn straws, sawdust, rice hulls and peanut shells, and the particle size of the biomass is 10-20 microns.
6. The method for preparing the solid acid catalyst based on the aluminous clinker-green carbon-based dual carrier as claimed in claim 1, wherein: the carbon-based matrix and concentrated sulfuric acid are uniformly mixed, wherein the volume ratio of the carbon-based matrix to the concentrated sulfuric acid is 10: 1-3, and the mass fraction of the concentrated sulfuric acid is 80-90%.
7. The method for preparing the solid acid catalyst based on the aluminous clinker-green carbon-based dual carrier as claimed in claim 1, wherein: the activated aluminum ash and the carbon-based precursor are uniformly mixed, and then 1, 4-dioxane is added, wherein the mass ratio of the activated aluminum ash to the carbon-based precursor is 1: 1-2, and the sum of the mass of the 1, 4-dioxane, the activated aluminum ash and the carbon-based precursor is 4:10 in terms of the volume mass ratio g: mL.
8. The method for preparing the solid acid catalyst based on the aluminous clinker-green carbon-based dual carrier as claimed in claim 1, wherein: and carrying out ultrasonic assisted dipping for 10-30 min, wherein the ultrasonic power is 80W.
9. The method for preparing the solid acid catalyst based on the aluminous clinker-green carbon-based dual carrier as claimed in claim 1, wherein: and heating to 400-600 ℃ in a nitrogen atmosphere, wherein the heating rate is 20 ℃/min.
10. The product prepared by the preparation method of the aluminous ash-green carbon-based dual-carrier-based solid acid catalyst as claimed in any one of claims 1 to 9, which is characterized in that: the specific surface area of the product is 216-352m2The diameter of the pore canal is 10-15 nm.
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