CN113368813A - Method for preparing honeycomb molecular sieve adsorbent by using red mud - Google Patents
Method for preparing honeycomb molecular sieve adsorbent by using red mud Download PDFInfo
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- CN113368813A CN113368813A CN202110856000.1A CN202110856000A CN113368813A CN 113368813 A CN113368813 A CN 113368813A CN 202110856000 A CN202110856000 A CN 202110856000A CN 113368813 A CN113368813 A CN 113368813A
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- molecular sieve
- honeycomb
- red mud
- sodium
- adsorbent
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 86
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000003463 adsorbent Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000003365 glass fiber Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 8
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 239000004014 plasticizer Substances 0.000 claims description 7
- 229920000193 polymethacrylate Polymers 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- -1 phthalic acid ester Chemical class 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical class CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical class [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical class CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 239000001913 cellulose Chemical class 0.000 claims description 2
- 229920002678 cellulose Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000013461 design Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000665 guar gum Substances 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims description 2
- 235000015110 jellies Nutrition 0.000 claims description 2
- 239000008274 jelly Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920001522 polyglycol ester Polymers 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 230000007306 turnover Effects 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 16
- 239000012855 volatile organic compound Substances 0.000 abstract description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000010457 zeolite Substances 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- 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
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/116—Molecular sieves other than zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/30—Physical properties of adsorbents
- B01D2253/34—Specific shapes
- B01D2253/342—Monoliths
- B01D2253/3425—Honeycomb shape
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Organic Chemistry (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for preparing a honeycomb-shaped molecular sieve adsorbent by using red mud, wherein the honeycomb-shaped molecular sieve adsorbent is prepared from the following raw materials: mixing the raw materials, pugging, extruding and forming, drying and roasting to obtain the honeycomb molecular sieve adsorbent. The invention realizes the recycling of the red mud solid waste, and the adsorbent has the advantages of high strength, large adsorption capacity and good regeneration effect, can be used for adsorbing industrial VOCs, reduces the production cost, can fully recycle a large amount of red mud, does not remain after roasting to influence the adsorption performance, improves the product quality, improves the fracture toughness of the honeycomb zeolite adsorbent, and ensures the integrity of the adsorbent.
Description
Technical Field
The invention relates to the technical field of molecular sieves, in particular to a method for preparing a honeycomb-shaped molecular sieve adsorbent by utilizing red mud.
Background
The molecular sieve is an aluminosilicate, a silicon-aluminum is connected through an oxygen bridge to form a hollow framework structure, a plurality of pore passages with uniform pore diameters and cavities with regular arrangement and large internal surface area are arranged in the structure, in addition, the molecular sieve also contains metal ions with lower electrovalence and larger ionic radius and water in a chemical state, because the water molecules are lost after being heated, but the crystal framework structure is not changed, a plurality of cavities with same giant fineness are formed, the cavities are connected by a plurality of micropores with same diameter, substance molecules with smaller diameter than the pore passages are adsorbed in the cavities, and the molecules larger diameter than the pore passages are extruded outside, so that the molecules with different giant fineness shapes are separated until the effect of sieving molecules is achieved, the molecular sieve is called, the red mud is industrial solid waste discharged after extracting the alumina from the bauxite, the yield of the alumina in China is large, and the amount of the red mud discharged each year reaches millions of tons, a large amount of red mud can not be fully and effectively utilized, can only be stacked by a large-area yard, occupies a large amount of land, and causes serious pollution to the environment.
At present, the preparation of the honeycomb molecular sieve VOCs adsorbent generally has two methods, one is a forming method, namely the adsorbent is mixed with a certain inorganic filler and extruded and formed into a honeycomb shape, but the mechanical strength is lower, and the adsorbent is fragile in the carrying process, the other is a coating method, namely the molecular sieve is coated on a honeycomb carrier, the prepared adsorbent has the characteristic of high mechanical strength, but the coating is easy to fall off, the coating effect directly influences the adsorption performance, and the application range of the molecular sieve is limited to a certain extent, secondly, the existing integral extrusion type honeycomb molecular sieve not only has few wall thickness and holes and more cracks, but also has low strength, large abrasion (easy powder falling), and low utilization rate of the molecular sieve, for a zeolite adsorption rotating wheel for VOCs purification, the hole density of the integral honeycomb molecular sieve of a core adsorption material is required to be more than or equal to 300 days, and the wall thickness is less than or equal to 0.25mm, and the patent technology related to the integral extrusion type honeycomb molecular sieve is described above, the requirements of the zeolite adsorption rotating wheel for purifying VOCs on the integral honeycomb molecular sieve are not met no matter the preparation method or the product specification of the integral extrusion honeycomb molecular sieve.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a method for preparing a honeycomb molecular sieve adsorbent by using red mud.
The invention provides a method for preparing a honeycomb molecular sieve adsorbent by using red mud, which comprises the following steps:
s1, mixing: putting raw powder of a molecular sieve, water, red mud, anti-crack glass fiber yarns and citric acid into a mixer in proportion, and stirring the raw materials for 1.5 hours by the mixer to fully mix the raw materials to obtain powder;
s2, pugging: putting the powder, water, an organic assistant, a plasticizer and a dispersant into a pug mill according to a certain proportion, and processing the powder into pug;
s3, molding: putting the pug into a vacuum extruder for extrusion molding to obtain a honeycomb-shaped molecular sieve raw material, wherein the extrusion pressure is 8-10 Mpa;
s4, drying: drying the formed honeycomb-shaped molecular sieve raw material at the temperature of 20-80 ℃ for 24 hours in a decompression drying mode, wherein the power is 250-650W;
s5, roasting: heating the dried honeycomb-shaped molecular sieve to 300 ℃ at the heating rate of 10-15 ℃/h, roasting for 2h, heating to 600 ℃ at the heating rate of 20-25 ℃/h, and roasting for 2h to obtain the complete honeycomb-shaped molecular sieve.
Preferably, the preparation process of the molecular sieve raw powder is as follows:
a. preparing sodium aluminate: adding 50g of liquid caustic soda or steaming mother liquor into a reaction kettle, heating the mixture under a stirring state, adding aluminum hydroxide after the temperature reaches the preparation temperature, adding an aluminum hydroxide solution at 120-150 ℃ to prepare sodium aluminate, adding 70g of mother liquor after the preparation is finished to adjust the concentration of the sodium aluminate solution to meet the raw material requirement for synthesizing the raw powder of the molecular sieve, and using the sodium aluminate solution after two-stage filtration for synthesizing the raw powder of the molecular sieve;
b. synthesizing: 6 kinds of materials are totally arranged in a synthesis section, namely liquid caustic soda, sodium aluminate, mother liquor, sodium silicate, water and a guiding agent, and the 6 kinds of materials are fed into a synthesis tank and are stirred for 1 hour;
c. aging and crystallizing: pumping the slurry in the synthesis tank into a crystallization tank after stirring, introducing steam for heating while stirring, controlling the heating temperature and the aging and crystallization time according to the process requirements, and stirring and discharging the material to enter a buffer tank after the reaction is finished;
d. mother liquor separation and washing: solid-liquid separation of the slurry is realized by a filter, filtrate is collected, washing and dewatering are carried out by wind pressure, the wind pressure is stopped when the attached water reaches 30-32%, and the filter cake enters a filter cake turnover bin e and is dried: and (4) drying the filter cake in drying equipment.
Preferably, the molecular sieve is formed by compounding microporous ZSM-5 and mesoporous ZSM-5 molecular sieves according to the mass ratio, the pore size distribution of the microporous ZSM-5 is 0-1nm, the pore size distribution of the mesoporous ZSM-5 is 1-5nm, the preliminarily prepared molecular sieve can be screened by a screening machine and a screen of 5-15mm, products with unqualified sizes in the molecular sieve are removed, a finished honeycomb-shaped molecular sieve can be obtained after screening, and the screening machine can be an HLQS-160 airflow type screening machine.
Preferably, the organic auxiliary agent is one or more of sodium humate, sodium polyacrylate and sodium polymethacrylate, the sodium humate is in a powder shape, the mass of the sodium humate is more than or equal to 150g, the sodium polyacrylate is in a block shape, the mass of the sodium polyacrylate is more than or equal to 30g, the sodium polymethacrylate is in a jelly shape, the mass of the sodium polymethacrylate is more than or equal to 100g, the plasticizer is one or more of phthalate, aliphatic dibasic acid ester, fatty acid ester, benzene polyacid ester, polyol ester, epoxy hydrocarbon and alkyl sulfonate, and the dispersant is one or more of triethyl hexyl phosphate, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, guar gum and fatty acid polyglycol ester.
Preferably, the average filament diameter of the anti-crack glass fiber is 10-30 μm, the average length is 0.5-1mm, and the anti-crack glass fiber can be divided into one or more of alkali-free, chemical-resistant, high-alkali, medium-alkali, high-strength, high elastic modulus and alkali-resistant (alkali-resistant) glass fiber.
Preferably, the reduced pressure drying process is to dry the honeycomb-shaped molecular sieve raw material after vacuumizing in a closed container, the honeycomb-shaped molecular sieve raw material can be flatly laid in the closed container, the drying equipment can be a YZG series vacuum dryer, the interlayer design pressure is 0.3Mpa, and the cylinder internal pressure is 0.092-0.096 Mpa.
Preferably, the roasting equipment can be a gas-fired rotary furnace, the furnace body is made of high-temperature alloy stainless steel and heat-resistant alloy steel, the rotating speed of the furnace tube is variable-frequency adjustable, and the inclination angle of the furnace body is 0-3 degrees.
Compared with the prior art, the invention has the following beneficial effects:
1. in the invention, the use range of the adsorbent is widened by the compound use of the micro mesoporous molecular sieve, and VOCs molecules with different particle sizes can be adsorbed, so that the adsorption of VOCs in the experimental process is more thorough and comprehensive, and the success rate of the experiment is ensured;
2. according to the invention, the red mud is used for replacing other inorganic fillers such as clay and the like to be mixed and molded, so that the recycling of solid wastes is realized, the production cost is reduced, a large amount of red mud can be fully recycled, the environment-friendly and energy-saving concept is met, and the raw materials can be fully utilized;
3. in the invention, the addition of the organic auxiliary agent can not only increase the plasticity of the pug, but also improve the drying strength of the blank, and meanwhile, the organic auxiliary agent does not remain after roasting to influence the adsorption performance, thereby improving the quality of the finished honeycomb molecular sieve and ensuring the experimental effect;
4. in the invention, the addition of the anti-crack glass fiber improves the fracture toughness of the honeycomb zeolite adsorbent, thereby ensuring the integrity of the prepared honeycomb molecular sieve finished product and preventing the molecular sieve finished product from fracturing and breaking.
Drawings
FIG. 1 is a graph showing the relationship between adsorption efficiency and adsorption time according to the present invention;
FIG. 2 is a graph showing the relationship between the outlet concentration and the adsorption time according to the present invention.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example one
The invention provides a method for preparing a honeycomb molecular sieve adsorbent by using red mud, which comprises the following steps:
s1, mixing: putting raw powder of a molecular sieve, water, red mud, anti-crack glass fiber yarns and citric acid into a mixer in proportion, and stirring the raw materials for 1.5 hours by the mixer to fully mix the raw materials to obtain powder;
s2, pugging: putting the powder, water, an organic assistant, a plasticizer and a dispersant into a pug mill according to a certain proportion, and processing the powder into pug;
s3, molding: putting the pug into a vacuum extruder for extrusion molding to obtain a honeycomb-shaped molecular sieve raw material, wherein the extrusion pressure is 8-10 Mpa;
s4, drying: drying the formed honeycomb-shaped molecular sieve raw material at the temperature of 20-80 ℃ for 24 hours in a decompression drying mode, wherein the power is 250-650W;
s5, roasting: heating the dried honeycomb-shaped molecular sieve to 300 ℃ at the heating rate of 10-15 ℃/h, roasting for 2h, heating to 600 ℃ at the heating rate of 20-25 ℃/h, and roasting for 2h to obtain the complete honeycomb-shaped molecular sieve.
In the embodiment, 80 parts of ZSM-5 molecular sieve raw powder, 3 parts of sodium humate, 20 parts of red mud, 3 parts of glass fiber and 2 parts of citric acid are added into a mixer to be uniformly mixed, then the mixed materials are put into a high-speed stirrer, 55 parts of water is added, the materials are uniformly stirred and then kneaded, wet mud is pugged for 3 times in a vacuum pug mill, then the mud is extruded and molded by a honeycomb hydraulic extruder to obtain a honeycomb blank, the honeycomb blank is dried for 24 hours at the temperature of 20-80 ℃, and the honeycomb blank is roasted for 4 hours at the temperature of 600 ℃ to obtain the adsorbent.
Example two
The invention provides a method for preparing a honeycomb molecular sieve adsorbent by using red mud, which comprises the following steps:
s1, mixing: putting raw powder of a molecular sieve, water, red mud, anti-crack glass fiber yarns and citric acid into a mixer in proportion, and stirring the raw materials for 2 hours by the mixer to fully mix the raw materials to obtain powder;
s2, pugging: putting the powder, water, an organic assistant, a plasticizer and a dispersant into a pug mill according to a certain proportion, and processing the powder into pug;
s3, molding: putting the pug into a vacuum extruder for extrusion molding to obtain a honeycomb-shaped molecular sieve raw material, wherein the extrusion pressure is 10-16 Mpa;
s4, drying: drying the formed honeycomb-shaped molecular sieve raw material at 22-82 ℃ for 18h in a reduced pressure drying mode with the power of 300-700W until the water content is less than or equal to 5.0 wt%;
s5, roasting: and (3) heating the dried honeycomb-shaped molecular sieve to 300 ℃ at the heating rate of 12-17 ℃/h, roasting for 1.5h, heating to 600 ℃ at the heating rate of 22-27 ℃/h, and roasting for 1.5h to obtain the complete honeycomb-shaped molecular sieve.
In the embodiment, 80 parts of ZSM-5 molecular sieve, 1 part of sodium polyacrylate, 25 parts of red mud, 3 parts of glass fiber and 2 parts of citric acid are added into a mixer to be uniformly mixed, then the mixed materials are put into a high-speed stirrer, 50 parts of water is added, the materials are uniformly stirred and then kneaded, wet mud is pugged for 3 times in a vacuum pug mill, then the mud is extruded and molded by a honeycomb hydraulic extrusion press to obtain a honeycomb blank, the honeycomb blank is dried for 18 hours at the temperature of 22-82 ℃, and the honeycomb blank is roasted for 3 hours at the temperature of 600 ℃ to prepare the adsorbent.
EXAMPLE III
The invention provides a method for preparing a honeycomb molecular sieve adsorbent by using red mud, which comprises the following steps:
s1, mixing: putting raw powder of a molecular sieve, water, red mud, anti-crack glass fiber yarns and citric acid into a mixer in proportion, and stirring the raw materials for 2.5 hours by the mixer to fully mix the raw materials to obtain powder;
s2, pugging: putting the powder, water, an organic assistant, a plasticizer and a dispersant into a pug mill according to a certain proportion, and processing the powder into pug;
s3, molding: putting the pug into a vacuum extruder for extrusion molding to obtain a honeycomb-shaped molecular sieve raw material, wherein the extrusion pressure is 12-18 Mpa;
s4, drying: drying the formed honeycomb-shaped molecular sieve raw material at 25-85 ℃ for 16h in a decompression drying mode with the power of 350-750W until the water content is less than or equal to 4.0 wt%;
s5, roasting: and (3) heating the dried honeycomb-shaped molecular sieve to 300 ℃ at the heating rate of 15-20 ℃/h, roasting for 1.3h, heating to 600 ℃ at the heating rate of 25-30 ℃/h, and roasting for 1.3h to obtain the complete honeycomb-shaped molecular sieve.
In the embodiment, 80 parts of ZSM-5 molecular sieve, 1 part of sodium polyacrylate, 1 part of sodium polymethacrylate, 30 parts of red mud, 2 parts of glass fiber and 1 part of citric acid are added into a mixer to be uniformly mixed, then the mixed materials are put into a high-speed stirrer, 50 parts of water is added to be uniformly stirred and kneaded, wet mud is pugged for 3 times in a vacuum pug mill, then the mud is extruded and molded by a honeycomb hydraulic extruder to obtain a honeycomb blank, the honeycomb blank is dried for 16 hours at the temperature of 25-85 ℃, and the honeycomb blank is roasted for 2.6 hours at the temperature of 600 ℃ to obtain the adsorbent.
Comparative example 1
Adding 80 parts of ZSM-5 molecular sieve, 15 parts of attapulgite, 15 parts of alumina and 3 parts of citric acid into a mixer, uniformly mixing, then putting the mixed materials into a high-speed stirrer, adding 50 parts of water, uniformly stirring, kneading, pugging wet pug for 3 times in a vacuum pug mill, then extruding and molding the pug by using a honeycomb hydraulic extruder to obtain a honeycomb blank, drying for 24 hours at 20-80 ℃, and roasting for 4 hours at 600 ℃ to obtain the adsorbent.
Comparative example 2
Adding 80 parts of ZSM-5 molecular sieve, 20 parts of kaolin, 10 parts of talcum powder and 2 parts of citric acid into a mixer, uniformly mixing, then putting the mixed materials into a high-speed stirrer, adding 50 parts of water, uniformly stirring, kneading, pugging wet pug for 3 times in a vacuum pug mill, then extruding and molding the pug by using a honeycomb hydraulic extruder to obtain a honeycomb blank, drying for 24 hours at 20-80 ℃, and roasting for 4 hours at 600 ℃ to obtain the adsorbent.
The compressive strength of the honeycomb molecular sieve adsorbent prepared above was tested, and the experimental results are shown in table 1.
TABLE 1
The adsorbent prepared in example 2 is used for adsorption purification of a mixture of various VOCs (volatile organic compounds) to simulate an adsorption experiment of an industrial fixed bed adsorption box, and the simulated gas of the mixture of various VOCs comes from a combination of paint and a diluent, and the composition of the simulated gas is shown in Table 2.
TABLE 2
The adsorption test conditions were as follows: the packing thickness is 500mm, the packing cross section area is 300mm, the wind speed is 2m/s, the waste gas inlet concentration is 300mg/m3, and the adsorption result is shown in figure 1 and figure 2.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention are equivalent to or changed within the technical scope of the present invention.
Claims (7)
1. A method for preparing a honeycomb molecular sieve adsorbent by using red mud is characterized by comprising the following steps:
s1, mixing: putting raw powder of a molecular sieve, water, red mud, anti-crack glass fiber yarns and citric acid into a mixer in proportion, and stirring the raw materials for 1.5 hours by the mixer to fully mix the raw materials to obtain powder;
s2, pugging: putting the powder, water, an organic assistant, a plasticizer and a dispersant into a pug mill according to a certain proportion, and processing the powder into pug;
s3, molding: putting the pug into a vacuum extruder for extrusion molding to obtain a honeycomb-shaped molecular sieve raw material, wherein the extrusion pressure is 8-10 Mpa;
s4, drying: drying the formed honeycomb-shaped molecular sieve raw material at the temperature of 20-80 ℃ for 24 hours in a decompression drying mode, wherein the power is 250-650W;
s5, roasting: heating the dried honeycomb-shaped molecular sieve to 300 ℃ at the heating rate of 10-15 ℃/h, roasting for 2h, heating to 600 ℃ at the heating rate of 20-25 ℃/h, and roasting for 2h to obtain the complete honeycomb-shaped molecular sieve.
2. The method for preparing the honeycomb-shaped molecular sieve adsorbent by using the red mud as claimed in claim 1, wherein the molecular sieve raw powder is prepared by the following steps:
a. preparing sodium aluminate: adding 50g of liquid caustic soda or steaming mother liquor into a reaction kettle, heating the mixture under a stirring state, adding aluminum hydroxide after the temperature reaches the preparation temperature, adding an aluminum hydroxide solution at 120-150 ℃ to prepare sodium aluminate, adding 70g of mother liquor after the preparation is finished to adjust the concentration of the sodium aluminate solution to meet the raw material requirement for synthesizing the raw powder of the molecular sieve, and using the sodium aluminate solution after two-stage filtration for synthesizing the raw powder of the molecular sieve;
b. synthesizing: 6 kinds of materials are totally arranged in a synthesis section, namely liquid caustic soda, sodium aluminate, mother liquor, sodium silicate, water and a guiding agent, and the 6 kinds of materials are fed into a synthesis tank and are stirred for 1 hour;
c. aging and crystallizing: pumping the slurry in the synthesis tank into a crystallization tank after stirring, introducing steam for heating while stirring, controlling the heating temperature and the aging and crystallization time according to the process requirements, and stirring and discharging the material to enter a buffer tank after the reaction is finished;
d. mother liquor separation and washing: the slurry is subjected to solid-liquid separation by a filter, filtrate is collected, washing and dehydration are carried out by wind pressure, the wind pressure is stopped when the attached water reaches 30-32%, and a filter cake enters a filter cake turnover bin;
e. and (3) drying: and (4) drying the filter cake in drying equipment.
3. The method for preparing the honeycomb-shaped molecular sieve adsorbent by using the red mud according to claim 1, wherein the molecular sieve is a compound of microporous ZSM-5 and mesoporous ZSM-5 molecular sieves in equal mass ratio, the pore size distribution of the microporous ZSM-5 is 0-1nm, the pore size distribution of the mesoporous ZSM-5 is 1-5nm, the preliminarily prepared molecular sieve can be screened by a screen of 5-15mm through a screening machine, products with unqualified sizes in the molecular sieve are removed, the finished honeycomb-shaped molecular sieve can be obtained after screening, and the screening machine can be an HLQS-160 airflow type screening machine.
4. The method for preparing the honeycomb-shaped molecular sieve adsorbent by using the red mud as claimed in claim 1, wherein the organic auxiliary agent is one or more of sodium humate, sodium polyacrylate and sodium polymethacrylate, the sodium humate is in a powder shape, the mass of the sodium humate is not less than 150g, the mass of the sodium polyacrylate is in a block shape, the mass of the sodium polyacrylate is not less than 30g, the sodium polymethacrylate is in a jelly shape, the mass of the sodium polymethacrylate is not less than 100g, the plasticizer is one or more of phthalic acid ester, aliphatic dibasic acid ester, fatty acid ester, benzene polyacid ester, polyol ester, epoxy hydrocarbon and alkyl sulfonate, and the dispersant is one or more of triethylhexyl phosphate, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivative, polyacrylamide, guar gum and fatty acid polyglycol ester.
5. The method for preparing the honeycomb-shaped molecular sieve adsorbent by using the red mud as claimed in claim 1, wherein the average monofilament diameter of the anti-crack glass fiber is 10-30 μm, the average length is 0.5-1mm, and the anti-crack glass fiber can be divided into one or more of alkali-free, chemical-resistant, high-alkali, medium-alkali, high-strength, high-elastic modulus and alkali-resistant glass fiber.
6. The method for preparing the honeycomb-shaped molecular sieve adsorbent by using the red mud as claimed in claim 1, wherein the reduced pressure drying process is to dry a honeycomb-shaped molecular sieve raw material after vacuumizing in a closed container, the honeycomb-shaped molecular sieve raw material can be flatly laid in the closed container, the drying equipment can be a YZG series vacuum dryer, the interlayer design pressure is 0.3Mpa, and the cylinder internal pressure is 0.092-0.096 Mpa.
7. The method for preparing the honeycomb-shaped molecular sieve adsorbent by using the red mud as claimed in claim 1, wherein the roasting equipment can be a gas-fired rotary furnace, the furnace body of the rotary furnace is made of high-temperature alloy stainless steel or heat-resistant alloy steel, the rotating speed of the furnace tube of the rotary furnace is variable-frequency adjustable, and the inclination angle of the furnace body is 0-3 degrees.
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