CN115178234A - Composite hierarchical pore catalysis-adsorption material and preparation method thereof - Google Patents
Composite hierarchical pore catalysis-adsorption material and preparation method thereof Download PDFInfo
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 claims abstract description 21
- 239000000429 sodium aluminium silicate Substances 0.000 claims abstract description 21
- 235000012217 sodium aluminium silicate Nutrition 0.000 claims abstract description 21
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 19
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 19
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 239000003463 adsorbent Substances 0.000 claims abstract description 12
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 11
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 11
- 229960000892 attapulgite Drugs 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 239000002994 raw material Substances 0.000 claims abstract description 6
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- 230000008025 crystallization Effects 0.000 claims description 12
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- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
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- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims 1
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 19
- 239000003054 catalyst Substances 0.000 abstract description 8
- 239000007789 gas Substances 0.000 description 32
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- 239000011593 sulfur Substances 0.000 description 29
- 229910052717 sulfur Inorganic materials 0.000 description 29
- 230000000694 effects Effects 0.000 description 14
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- 238000000034 method Methods 0.000 description 12
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- 239000000047 product Substances 0.000 description 7
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- 125000001741 organic sulfur group Chemical group 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
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- -1 monocyclic aromatic hydrocarbon Chemical class 0.000 description 2
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- 230000008092 positive effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
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- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 238000009628 steelmaking Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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- 238000004056 waste incineration Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention relates to the technical field of industrial adsorbent preparation, and discloses a preparation method of a composite hierarchical pore catalysis-adsorption material, which comprises the following steps: pseudo-boehmite, sodium aluminosilicate, kaolin, attapulgite, metal salt and graphene oxide are used as raw materials, hydrothermal crystallization is carried out, and then products of the hydrothermal crystallization are subjected to suction filtration, washing, drying and roasting to obtain the composite type hierarchical pore catalysis-adsorption material. The composite catalytic-adsorption material forms a catalyst carrier with hierarchical pores, the pore diameter range of the catalyst carrier is expanded, and the catalytic-adsorption function of the material is improved.
Description
Technical Field
The invention relates to a composite hierarchical pore catalysis-adsorption material and a preparation method thereof, belonging to the technical field of industrial adsorbent preparation.
Background
Sulfur-containing gases (e.g. H) 2 S、CS 2 COS, mercaptans, thioethers, thiophenes etc.) mainly from the metallurgical, chemical, oil refining, mining, waste incineration, boilers, automobiles etc. industries, the direct emission of sulfur-containing gases without desulfurization would harm human health and destroy the ecological environment, while the direct use of valuable sulfur-containing gases would severely corrode production equipment.
Taking blast furnace gas as an example, the blast furnace gas is a byproduct gas in the steel making process, and the quantity of the blast furnace gas is about 1300-1600 m per ton of produced steel iron 3 Blast furnace gas is generated, contains about 23 percent of CO and can be used for synthesizing products such as methanol, glycol and the like. At present, iron and steel enterprises at home and abroad generally firstly utilize a dry dedusting and residual pressure turbine power generation device (TRT) to fully recover pressure energy and heat energy in blast furnace gas, and then send the blast furnace gas after energy recovery by the TRT device to users such as a hot blast stove, a heating furnace, a coke oven, a boiler, sintering, pellets and the like to be used as fuel. The total sulfur content in the blast furnace gas is about 60-160 mg/m 3 Containing inorganic sulfur (mainly H) 2 S) and organic sulfur, wherein H 2 S accounts for about 5-10%, COS and CS 2 The organic sulfur accounts for 90-95 percent, and the COS and CS in the organic sulfur 2 Accounts for more than 90 percent. The blast furnace gas directly used by the TRT device to recover energy without further desulfurization treatment can cause the corrosion of pipelines and equipment, and even leakage and explosion accidents. China stipulates that: the small-hour average value of the sulfur dioxide emission concentration of the head of the sintering machine, the pellet roasting flue gas and the self-contained power plant gas boiler is not higher than 35mg/m 3 The sulfur dioxide emission concentration of the hot blast stove and the heat treatment furnace is not higher than 50mg/m 3 This suggestion further improves the standard of desulfurization of blast furnace gas.
Is at present widely usedThe methods used for desulfurization of sulfur-containing gases are hydroconversion, wet desulfurization and dry desulfurization. The hydro-conversion method has the advantages of high process pressure, high temperature, high energy consumption, short service life of the adsorbent, large annual replacement amount, time and labor consumption, high temperature of the wet desulphurization process, short service life of the catalyst and generation of solid waste. Dry desulfurization mainly uses solid adsorbents such as activated carbon, iron oxide, zinc oxide, molecular sieves and the like. The sulfide is absorbed and removed, after the absorbent is saturated, a small amount of clean product gas is usually extracted as regeneration desorption gas, the absorbed sulfide is desorbed and converted after heating, and the absorbent is regenerated. Compared with wet desulphurization, dry desulphurization has the advantages of low cost, strong adsorbent regeneration capacity, long service life and the like. For example, the patent application with publication number CN110819393A discloses a method and a device for fine desulfurization and purification of blast furnace gas, which comprises the steps of conversion, cooling and adsorption, wherein a molecular sieve is adopted as an adsorption material in an adsorption unit in the adsorption step, and the total sulfur concentration of the purified gas obtained after adsorption is less than 30mg/Nm 3 . Although the method can achieve the effect of effectively removing the sulfides in the blast furnace gas, the commercial molecular sieve has fixed volume and shape and limited specific surface area, so that the adsorption capacity is small, the further adsorption of the commercial molecular sieve on the sulfides is limited, the deep desulfurization cannot be realized, the later period of desorption and regeneration is frequent, the energy consumption is high, and the desulfurization efficiency is low.
Disclosure of Invention
The invention aims to provide a composite hierarchical pore catalysis-adsorption material and a preparation method thereof, the catalysis-adsorption material has high desulfurization efficiency, and solves the problem that the adsorption capacity is smaller due to the fact that the volume and the shape of the conventional commercial molecular sieve are fixed and the specific surface area is limited.
The invention is realized by the following technical scheme:
a preparation method of a composite hierarchical pore catalysis-adsorption material comprises the following steps: pseudo-boehmite, sodium aluminosilicate, kaolin, attapulgite, metal salt and graphene oxide are used as raw materials, hydrothermal crystallization is carried out, and then products of the hydrothermal crystallization are subjected to suction filtration, washing, drying and roasting to obtain the composite type hierarchical pore catalysis-adsorption material.
Further, before hydrothermal crystallization, graphene oxide is dispersed in a solvent, then metal salt is added under the stirring condition to prepare a mixed solution, and then pseudo-boehmite, sodium aluminosilicate, kaolin and attapulgite are added into the mixed solution to carry out hydrothermal crystallization.
Further, the solvent is deionized water or ethanol.
Furthermore, the temperature of the hydrothermal crystallization treatment is 100-150 ℃, and the crystallization time is 12-72h. Preferably, the hydrothermal crystallization treatment comprises two stages: the first stage is that the temperature is firstly raised to 100-120 ℃, and crystallization is carried out for 6-8 h under continuous stirring; the second stage is that after the reaction in the first stage is finished, the temperature is raised to 140-150 ℃, the crystallization is carried out for 6-64 h under slow stirring, the stirring speed in the first stage is 500-600 rpm, and the stirring speed in the second stage is 300-400 rpm.
According to the technical scheme, low-temperature crystallization is carried out firstly, so that powdery pseudo-boehmite, sodium aluminosilicate, kaolin and attapulgite can be loaded on graphene oxide firstly, and high-temperature crystallization is carried out later, so that the multistage carrier is continuously crystallized to load metal ions, and the material of the composite carrier for loading metal active components is obtained.
Further, freeze drying is adopted for drying, the drying temperature is-80 to-20 ℃, and the drying pressure is normal pressure or negative pressure.
Further, the roasting temperature is 450-750 ℃; preferably, the calcination atmosphere is air or nitrogen or CO 2 Atmosphere, roasting pressure is normal pressure or negative pressure.
Furthermore, the raw materials comprise pseudo-boehmite, metal salt, sodium aluminosilicate, kaolin, attapulgite and graphene oxide according to the mass ratio of (5-30) to (5-10) to (50-80) to (10-20) to (5-10) to (5-30).
Further, the metal salt is selected from at least one of nitrate or chloride of magnesium, calcium and zinc.
Further, the composite hierarchical pore catalysis-adsorption material is obtained by the preparation method of the composite hierarchical pore catalysis-adsorption material.
Further, the composite type hierarchical pore catalysis-adsorption material is strip-shaped, spherical or rod-shaped.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. four inorganic aluminum sources of pseudo-boehmite, sodium aluminosilicate, kaolin and attapulgite with high specific surface area and large pore volume are adopted as a composite catalyst carrier, so that a catalyst carrier with multistage pores can be formed, the pore size range of the catalyst carrier is enlarged, and the catalysis-adsorption function of the catalyst carrier is improved;
2. the composite hierarchical pore catalysis-adsorption material has the functions and effects that: (1) the conversion function of carbonyl sulfide and carbon disulfide to hydrogen sulfide is improved, the hydrolysis reaction efficiency is improved by the adsorption heat, (2) the physical adsorption and weak chemical adsorption functions of hydrogen sulfide are improved, and the reverse reaction of oxidation and hydrolysis of hydrogen sulfide is prevented (the effect of sodium aluminosilicate), (3) the hierarchical pores provide reasonable mass transfer and internal diffusion performance, (4) the composite multi-stage catalytic carrier is enriched on graphene oxide, and graphene oxide provides a bearing unit and a fixing unit of the catalytic carrier, so that four aluminum sources in a final roasting product are combined more tightly and have good tightness, the wear-resisting and pressure-resisting functions are improved, meanwhile, the flat structure of graphene oxide provides a flat bearing unit with good four aluminum sources, so that the composite multi-stage pore catalytic-adsorption material has a large specific surface area and better catalytic-adsorption performance, (5) the easy regeneration function (the effect of sodium aluminosilicate), (6) the water-resisting performance (the effect of sodium aluminosilicate), (7) the composite multi-stage catalytic-adsorption material has strong adaptability, and can be used for modulating the performance of the composite multi-stage catalytic-stage adsorption material according to different desulfurization atmospheres; 3. the composite type multi-stage pore catalytic-adsorption material has both the function of converting organic sulfur and the function of adsorbing/desorbing aromatic hydrocarbon compounds and inorganic sulfur. The composite hierarchical pore catalysis-adsorption material converts part of organic sulfur into inorganic sulfur, is adsorbed and captured, has weak chemical adsorption effect on monocyclic aromatic hydrocarbon, polycyclic aromatic hydrocarbon and inorganic sulfur, is easy to desorb and regenerate, and can be used for deep purification of blast furnace gas, coke oven gas and sulfur-containing flue gas/tail gas.
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 are 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 creative efforts.
Fig. 1 is an SEM image of rGO, multi-stage support/rGO material;
fig. 2 is a BET diagram of a multi-stage support/rGO composite multi-stage pore catalytic-adsorption material.
Detailed Description
Examples 1 to 5
Examples 1 to 5 provide a method for producing a composite type hierarchical pore catalytic-adsorbing material (a metal ion is used as a catalytic active component — a hierarchical aluminum source supported on graphene oxide is used as a hierarchical catalyst carrier, and the composite type hierarchical pore catalytic-adsorbing material is simply represented by a hierarchical carrier/rGO below) including the steps of:
firstly, weighing materials according to the mass ratio of pseudo-boehmite to metal salt to sodium aluminosilicate to kaolin to attapulgite to graphene oxide of (5-30) to (5-10) to (50-80) to (10-20) to (5-10) to (5-30), wherein all the materials are selected from powdery materials as raw materials, wherein the metal salt is taken as a basic amount to be weighed for 50g, and the specific selection of the metal salt is shown in Table 1;
secondly, dispersing the weighed graphene oxide in a solvent, and then adding metal salt under the condition of continuous stirring to prepare a mixed solution; the solvent is deionized water; continuous stirring can also be replaced by ultrasonic treatment;
thirdly, adding pseudo-boehmite, sodium aluminosilicate, kaolin and attapulgite into the mixed solution for hydrothermal crystallization, stirring at 400rpm for crystallization for 24 hours, and then carrying out suction filtration, washing, drying and roasting on a product of the hydrothermal crystallization to obtain the composite hierarchical pore catalytic-adsorption material; the temperature of the hydrothermal crystallization treatment is 100-150 ℃ and the crystallization time is 12-72h, wherein the hydrothermal crystallization in example 5 is carried out in two stages, the first stage is to raise the temperature to 100 ℃, and the crystallization is carried out for 6h under the stirring of 500rpm, the second stage is to increase the temperature to 100 ℃In the second stage, the temperature is raised to 150 ℃, and crystallization is carried out for 24 hours under the stirring of 400 rpm; the suction filtration and washing are carried out by using deionized water so as to better remove nitrate ions and chloride ions; freeze drying is adopted for drying, the drying temperature is-80 to-20 ℃, and the drying pressure is normal pressure or negative pressure; the roasting temperature is 450-750 ℃; the roasting atmosphere is air or nitrogen or CO 2 Atmosphere, roasting pressure is normal pressure or negative pressure.
TABLE 1 values of specific parameters of examples 1-5
Specific parameter values of examples 1 to 5 are shown in table 1, and SEM images of the composite porous catalytic-adsorbent material obtained in example 5 are shown in fig. 1: fig. 1a and 1b are SEM images of a product rGO after roasting of GO dissolved in a solvent, fig. 1c and 1d are SEM images of a multi-stage support/rGO product in example 5, fig. 1d is a partially enlarged view of fig. 1c, it can be seen from the figures that a composite material is composed of a two-dimensional rGO (reduced graphene oxide) lamellar structure supporting a multi-stage pore catalytic support and a metal active component, and fig. (d) shows a clearer reaction pore structure, which indicates that the original structure of rGO is not damaged by the composite.
Fig. 2 is a BET plot of the multi-stage support/rGO composite multi-stage pore catalytic-adsorbent material of example 5: it can be seen in fig. 2a that the multi-stage support, rGO, multi-stage support/rGO composite catalytic-adsorbent material has a large hysteresis loop, belonging to type IV adsorption-desorption isotherms according to IUPAC, caused by the porous structure present in the sample. Therefore, the adsorption characteristics of nitrogen are poor when the three samples are in P/P0=0.45-1.00, and the hysteresis cycle indicates that pores exist, which indicates that the multi-stage carrier has porosity. From FIG. 2b, it can be seen that the pore diameters of the multilevel carrier are mainly distributed at 2-50nm, the medium and large pores are less, the pore diameter of rGO is 2-5nm, and the pore diameter of the multilevel carrier/rGO composite is 2-8nm, which indicates that the composite material of the embodiment of the present invention maintains the original porous structure.
Examples 6 to 10
The following preparation was carried out, likewise in accordance with the procedure described above, based on example 5The parameters of examples 6-10 differ from example 5 in the mass ratio of the multi-stage support/rGO material, in that the corresponding contents of the components put into the support are different, see in particular table 2, and the other parameters are the same as in example 5. The prepared catalytic-adsorption material is used for desulfurizing mixed gas, the mixed gas adopts blast furnace gas and comprises the following components: CH (CH) 4 ：0.4％；CO 2 ：1-20％；CO：24％；O 2 ：0.3％；H 2 ：5％；H 2 S：100ppm； COS：80ppm；H 2 O: 5% (saturated water); balance gas N 2 . At a temperature of 40-60 ℃, the volume of the catalytic-adsorption material is 10mL, and the space velocity: 300-1000h -1 The test was performed under the conditions.
TABLE 2 part of the experimental parameters and adsorption results of examples 1-10
As can be seen from Table 2, the penetration sulfur capacity of the composite hierarchical pore catalytic-adsorption material prepared by the method to blast furnace gas is kept at a high level (2-4 g/100 g), which indicates that the catalytic-adsorption performance of the catalytic-adsorption material is improved by the compounding of the multilevel carrier. Analysis examples 1 to 5 show that the sulfur penetration capacity of the composite type hierarchical pore catalytic-adsorption material prepared by the method is kept at a high level in the presence of the flat carrier reduced graphene oxide. Analysis example 6 shows that, in the absence of a flat carrier for reducing graphene oxide, the penetration sulfur capacity of the obtained material is significantly reduced, which indicates that the composite carrier may be agglomerated or the pores are closed, but the penetration sulfur capacity still reaches 0.2g/100g, which indicates that the composite carrier still has a good porous diameter distribution effect and still has a positive effect on the penetration sulfur capacity. Analysis examples 7-10 show that the sulfur breakthrough capacity of the catalytic-adsorbing material prepared in the absence of pseudo-boehmite or in the absence of sodium aluminosilicate is lower than that of the composite catalytic-adsorbing material with four carriers, which indicates that the carriers have a negative effect on the sulfur breakthrough capacity, and this is the reason why the adsorption effect is not good due to the lack of a gradient of pore size. Analysis examples 5, 9 and 10 show that, under the same mass of the whole substance, the breakthrough sulfur capacity of the composite catalytic-adsorption material prepared by simultaneously adding the pseudo-boehmite and the sodium aluminosilicate is higher than that of the composite catalytic-adsorption material prepared by only adding the same mass of the pseudo-boehmite or the same mass of the sodium aluminosilicate, which indicates that the pseudo-boehmite and the sodium aluminosilicate in the composite hierarchical porous catalytic-adsorption material have a synergistic effect and have a better catalytic-adsorption effect on the composite material.
Examples 11 to 16
Test examples of the following mass ratios of multi-stage support/rGO material were prepared, also according to the procedure described above, based on example 5, with the parameters of examples 11-15 differing from those of example 5 in the content of the ingredients charged to the support, see in particular table 3, and with the other parameters being the same as those of example 5 and differing from those of examples 6-10 in the environment in which the breakthrough sulfur capacity test was carried out. The catalytic-adsorption materials (examples 1 to 5 and examples 11 to 15) thus obtained were used for the desulfurization of a gas mixture, which was coke oven gas and had the following composition: CH (CH) 4 ：24％；CO 2 ：3％；CO：10％；O 2 ：0.3％；N 2 ：5％；H 2 S: 80ppm; COS:40ppm; H2O: 5% (saturated water); balance gas H 2 . At a temperature of 30-50 ℃, the volume of the catalytic-adsorption material is 10mL, and the space velocity: 300-1000h -1 The test was performed under the conditions.
TABLE 3 part of the experimental parameters and adsorption results of examples 11 to 15
As can be seen from Table 3, the penetration sulfur capacity of the composite hierarchical pore catalytic-adsorption material prepared by the method for blast furnace gas is kept at a high level (2.3-3.9 g/100 g), which indicates that the catalytic-adsorption performance of the catalytic-adsorption material is improved by the compounding of the multilevel carrier. Analysis examples 1 to 5 show that the sulfur penetration capacity of the composite type hierarchical pore catalytic-adsorption material prepared by the method is kept at a high level in the presence of the flat carrier reduced graphene oxide. Analysis example 11 shows that, due to the lack of the flat carrier for reducing graphene oxide, the sulfur penetration capacity of the obtained material is significantly reduced, which indicates that the composite carrier may be agglomerated or have pores closed, but the sulfur penetration capacity still reaches 0.4g/100g, which indicates that the composite carrier still has a good porous distribution effect and still has a positive effect on the sulfur penetration capacity. Analysis examples 11 to 15 show that the sulfur permeability of the catalytic-adsorbent material prepared in the absence of the pseudo-boehmite or in the absence of the sodium aluminosilicate is lower than that of the composite catalytic-adsorbent material having all four carriers, which indicates that the carriers having less sulfur permeability have a negative effect on the sulfur permeability, and this is the reason why the adsorption effect is not good due to the less gradient of the pore size. Analysis examples 5, 14 and 15 show that, under the same mass of the whole substance, the breakthrough sulfur capacity of the composite catalytic-adsorption material prepared by simultaneously adding the pseudo-boehmite and the sodium aluminosilicate is higher than that of the composite catalytic-adsorption material prepared by only adding the same mass of the pseudo-boehmite or the same mass of the sodium aluminosilicate, which indicates that the pseudo-boehmite and the sodium aluminosilicate in the composite hierarchical porous catalytic-adsorption material generate a synergistic effect and have a better catalytic-adsorption effect on the composite material.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.
Claims (10)
1. The preparation method of the composite hierarchical pore catalysis-adsorption material is characterized by comprising the following steps: pseudo-boehmite, sodium aluminosilicate, kaolin, attapulgite, metal salt and graphene oxide are used as raw materials, hydrothermal crystallization is carried out, and then products of the hydrothermal crystallization are subjected to suction filtration, washing, drying and roasting to obtain the composite type hierarchical pore catalysis-adsorption material.
2. The preparation method of the composite hierarchical pore catalytic-adsorption material according to claim 1, wherein graphene oxide is dispersed in a solvent before hydrothermal crystallization, then a metal salt is added under stirring to prepare a mixed solution, and then pseudo-boehmite, sodium silicoaluminate, kaolin and attapulgite are added into the mixed solution to perform hydrothermal crystallization.
3. The preparation method of the composite hierarchical pore catalytic-adsorption material according to claim 2, wherein the solvent is deionized water or ethanol.
4. The preparation method of the composite type hierarchical pore catalytic-adsorption material according to claim 1, wherein the temperature of the hydrothermal crystallization treatment is 100-150 ℃, and the crystallization time is 12-72h;
preferably, the hydrothermal crystallization treatment comprises two stages: in the first stage, the temperature is firstly increased to 100 to 120 ℃, and crystallization is carried out for 6 to 8h under continuous stirring; and the second stage is that after the reaction in the first stage is finished, the temperature is increased to 140 to 150 ℃, the crystallization is carried out for 6 to 64h under the condition of slow stirring, the stirring speed in the first stage is 500 to 600rpm, and the stirring speed in the second stage is 300 to 400rpm.
5. The preparation method of the composite hierarchical pore catalytic-adsorption material according to claim 1, wherein the drying is performed by freeze drying at-80 to-20 ℃ under normal pressure or negative pressure.
6. The preparation method of the composite type hierarchical pore catalytic-adsorption material according to claim 1, wherein the roasting temperature is 450-750 ℃; preferably, the calcination atmosphere is air or nitrogen or CO 2 Atmosphere, roasting pressure is normal pressure or negative pressure.
7. A preparation method of the composite hierarchical pore catalytic-adsorption material according to any one of claims 1 to 6, characterized in that the raw materials comprise pseudo-boehmite, metal salt, sodium aluminosilicate, kaolin, attapulgite and graphene oxide in a mass ratio of (5-30): (5-10): (50-80): (10-20): (5-10): (5-30).
8. A preparation method of the composite type hierarchical pore catalytic-adsorption material according to claim 7, wherein the metal salt is selected from at least one of nitrates or chlorides of magnesium, calcium and zinc.
9. A composite type hierarchical pore catalysis-adsorption material, which is obtained by the preparation method of the composite type hierarchical pore catalysis-adsorption material of any one of claims 1 to 8.
10. A composite porous catalytic-adsorbent material according to claim 9, wherein said catalytic-adsorbent material is in the form of strips, spheres or rods.
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