CN114011408A - Process method for treating carbon fiber production process waste gas with molecular sieve catalyst - Google Patents
Process method for treating carbon fiber production process waste gas with molecular sieve catalyst Download PDFInfo
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- CN114011408A CN114011408A CN202111118750.5A CN202111118750A CN114011408A CN 114011408 A CN114011408 A CN 114011408A CN 202111118750 A CN202111118750 A CN 202111118750A CN 114011408 A CN114011408 A CN 114011408A
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- molecular sieve
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- carbon fiber
- waste gas
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- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 101
- 230000008569 process Effects 0.000 title claims abstract description 84
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 71
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 71
- 239000002912 waste gas Substances 0.000 title claims abstract description 68
- 238000007380 fibre production Methods 0.000 title claims abstract description 67
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 43
- 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 43
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 150000003624 transition metals Chemical class 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 119
- 239000007789 gas Substances 0.000 claims description 54
- 238000001035 drying Methods 0.000 claims description 26
- 239000010949 copper Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 231100000252 nontoxic Toxicity 0.000 claims description 3
- 230000003000 nontoxic effect Effects 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 150000003623 transition metal compounds Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 46
- 229910001868 water Inorganic materials 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- 238000007084 catalytic combustion reaction Methods 0.000 description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 229910052593 corundum Inorganic materials 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 description 15
- 239000007795 chemical reaction product Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 14
- 238000004868 gas analysis Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 230000003287 optical effect Effects 0.000 description 14
- 238000004445 quantitative analysis Methods 0.000 description 14
- 239000010453 quartz Substances 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 13
- 238000001704 evaporation Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000001514 detection method Methods 0.000 description 12
- 238000011068 loading method Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 229910017767 Cu—Al Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000011363 dried mixture Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010819 recyclable waste Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/24—Iron group metals or copper
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
- B01J29/68—Iron group metals or copper
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7676—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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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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- Chemical Kinetics & Catalysis (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
一种分子筛催化剂处理碳纤维生产工艺废气的工艺方法，属于为废气处理领域，其中以ZSM‑5、Beta、SSZ‑13、Y、ZSM‑35、MOR、MCM‑22、MCM‑49分子筛中至少一种为载体，以过渡金属Cu、Co、Fe、Mn、Ni中的一种或几种为活性中心，催化剂在较低温度下同时脱除多种有害组分，且具有较高的催化净化活性和产物氮气选择性。A process method for a molecular sieve catalyst to treat carbon fiber production process waste gas, belonging to the field of waste gas treatment, wherein at least one of ZSM-5, Beta, SSZ-13, Y, ZSM-35, MOR, MCM-22, MCM-49 molecular sieves is used. It uses one or more of transition metals Cu, Co, Fe, Mn and Ni as the active center. The catalyst simultaneously removes a variety of harmful components at low temperature and has high catalytic purification activity. and product nitrogen selectivity.
Description
Technical Field
The invention belongs to the field of waste gas purification, and particularly relates to an application and a treatment method of a molecular sieve catalyst for simultaneously treating multiple harmful components in waste gas in a carbon fiber production process.
Technical Field
The carbon fiber has the characteristics of high strength, high modulus, high temperature resistance, corrosion resistance, fatigue resistance, creep resistance, excellent electric conduction and heat conduction performance and the like, and becomes an indispensable engineering material for military and aerospace industries since the 50 th century. In the production process of Polyacrylonitrile (PAN) -based carbon fiber, crosslinking, cyclization and thick cyclization occur in and among PAN molecules, disordered-layer graphite structures are gradually formed, and a large amount of volatile small-molecule substances (such as HCN and NH) are generated3、CO、CO2、H2、 N2Etc.) to form carbon fiber production process off-gas. Wherein HCN, NH3And CO is a highly toxic and highly polluted gas, and if the CO is directly discharged, atmospheric pollution is caused, so that the human health is threatened, and even the life is threatened.
Currently, the current practice is. There are four main methods for treating waste gas from carbon fiber production processes: absorption, adsorption, direct combustion and catalytic combustion. The post-treatment process of the absorption waste liquid generated by the absorption method is complex, and the operation cost is high; the adsorption method needs frequent replacement or regeneration of the adsorbent due to the limited adsorption capacity of the adsorption material, so that the equipment occupies a large area; the reaction condition of the direct combustion method is high temperature of more than 800 ℃, and NO is easily generatedxSecondary pollution is formed, a large amount of combustion improver (diesel oil or natural gas) is consumed, and the process cost and the energy consumption are high. The catalytic combustion method is characterized in that under the action of a catalyst, various harmful components in waste gas generated in the carbon fiber production process react with oxygen at low temperature (200-400 ℃), and are selectively catalytically oxidized into N2、CO2And H2O, and the like. The method has the advantages of low ignition temperature, no secondary pollution, recyclable waste heat, convenient operation and management, low running cost and the like, and has a very promising prospect.
The key technology of the catalytic combustion method is to develop an efficient catalyst aiming at different technological processes. CN1404900A, CN1404904A and CN1404905A adopt catalysts mainly comprising single or multiple proportioning metals of platinum, palladium and rhodium, CN1416950A adopts a catalyst loaded with platinum metal and taking alumina as a carrier, but the noble metal is expensive and the cost of the catalyst is higher, and the exhaust gas on the catalyst is completely oxidized to generate NOxSecondary pollution is formed. The CN107913725A adopts a copper oxide catalyst loaded by taking titanium oxide and SBA-15 as a composite carrier, and the CN102734812 adopts a transition metal loaded mesoporous molecular sieve catalyst, so that although the cost of the catalyst is reduced, the removal efficiency is low, and the selectivity of the product nitrogen is not high.
In addition, in the prior art, the removed harmful component gas only aims at one component of HCN in the carbon fiber production process waste gas, and the application of the catalyst for simultaneously treating multiple harmful components in the carbon fiber production process waste gas under the low-temperature condition is not reported.
Disclosure of Invention
The technical problem to be solved by the invention is that the existing catalyst can not simultaneously treat various harmful components (HCN, CO and NH)3) The catalyst can simultaneously treat a plurality of harmful components in the waste gas of the carbon fiber production process under the condition of low temperature and convert the harmful components into N2、CO2And H2O, and the product nitrogen has high selectivity, and the treated tail gas basically does not contain NOx. The catalyst has the advantages of simple raw materials, low cost, no by-product, no pollution and industrial application value.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the application of a molecular sieve catalyst for simultaneously treating a plurality of harmful components in waste gas generated in a carbon fiber production process is disclosed, wherein the molecular sieve catalyst comprises the following components in 100 parts by weight:
(1) 90-99.9 parts of a catalyst molecular sieve carrier;
(2) 0.1-10 parts of transition metal; wherein the mass ratio of the carrier to the transition metal is preferably 95: 5.
In the technical scheme, the molecular sieve carrier is formed by compounding at least one or more of ZSM-5, Beta, SSZ-13, Y, ZSM-35, MOR, MCM-22 and MCM-49, and is preferably ZSM-5.
In the above technical solution, the silica-alumina ratio of the molecular sieve support is preferably 2 to + ∞, and is preferably 30.
In the above technical solution, the transition metal active component is selected from one or more of Cu, Co, Fe, Mn, or Ni, preferably Cu.
In the above technical scheme, the catalyst can be prepared by a method comprising the following steps:
and fully mixing the solution containing the transition metal compound with the selected molecular sieve carrier, drying and roasting to prepare the catalyst.
When the active component comprises Cu, the compound of Cu can be selected from one or more of copper nitrate, copper acetate and the like.
When the active component comprises CoWhen, C is saidoThe compound (B) can be selected from one or more of cobalt nitrate, cobalt chloride and the like.
When the active component comprises Fe, the compound of Fe can be selected from one or more of ferric nitrate, ferric chloride and the like.
When the active component comprises Mn, the Mn compound can be selected from one or more of manganese nitrate, manganese acetate and the like.
When the active component comprises Ni, the compound of Ni can be one or more selected from nickel nitrate, nickel chloride and the like.
In the above preparation method, the drying method is not particularly limited, for example, but not limited to, the drying temperature is 50 to 110 ℃, and the drying time is not particularly limited, for example, but not limited to, 0.5 to 24 hours.
In the preparation method, the roasting process conditions are not particularly limited, for example, but not limited to, the roasting temperature rise rate is 1-20 ℃/min, the roasting temperature is 300-800 ℃, and the roasting time is, for example, but not limited to, 2-10 hours.
When the molecular sieve catalyst is used for treating waste gas generated in the carbon fiber production process, the reaction temperature range of the waste gas treatment is 0-1000 ℃, preferably 200-600 ℃, and further preferably 350 ℃.
In the technical scheme, the method for simultaneously treating various harmful components in the waste gas of the carbon fiber production process comprises HCN and NH3CO to N2、CO2、H2O is a nontoxic and harmless product.
In the technical scheme, waste gas and O in the carbon fiber production process2The total feeding volume meter has the airspeed of 1000-100000 h-1Preferably 20000h-1。
The invention has the following effects:
aiming at various harmful components contained in waste gas in the carbon fiber production process, the catalyst provided by the invention selects cheap and easily-obtained transition metal as an active component, selects a series of molecular sieves with regular pore channel structures and higher specific surface areas as carriers, and designs a preparation method which is convenient and simple to operate, so that various harmful components in waste gas in the carbon fiber production process are efficiently converted into N at lower temperature2、CO2、H2O is a nontoxic and harmless product and has no secondary pollution. For example, in example 1, the optimum reaction temperature on the prepared catalyst was 350 ℃, at which point the HCN conversion reached 100%, NH3The conversion rate reaches 99%, the CO conversion rate reaches 100%, and the yield of N2 reaches 97.30%.
Drawings
FIG. 1 is an x-ray diffraction pattern of the catalysts and molecular sieve supports of examples 1-10.
FIG. 2 shows catalysts H of examples 7 to 102And (5) performing temperature programmed desorption characterization results.
FIG. 3 shows the results of the nitrogen adsorption/desorption characterization of the catalysts of examples 1-10.
FIG. 4 shows the conversion rate and N of catalysts of examples 1, 7-10 for catalytic combustion of various harmful components in waste gas from carbon fiber production process2Yield as a function of temperature.
FIG. 5 shows the conversion rate and N of catalysts of examples 1-6 for catalytic combustion of various harmful components in the exhaust gas process of carbon fiber production2Yield as a function of temperature.
FIG. 6 shows production of carbon fibers by catalysts of examples 1, 11 to 14Conversion rate and N of catalytic combustion of multiple harmful components in process waste gas2Yield as a function of temperature.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
As an embodiment, the carbon fiber production process waste gas in the following examples of the present invention was simulated by mixing various standard gases (HCN: 400ppm, NH)3: 2500ppm, CO: 1000ppm, Ar: balance gas).
[ example 1 ]
1. Catalyst preparation
A certain amount of copper nitrate (weighed according to the loading amount of 5% by mass of Cu) is dissolved in 200ml of deionized water to prepare a solution, and 2.0g of SiO is weighed2/Al2O3Mixing the solution with an H-ZSM-5 molecular sieve of 30 percent, fully stirring the mixture for 8 hours in a water bath kettle at the temperature of 40 ℃, slowly evaporating the water in the solution by using a rotary vacuum evaporator, drying the solution for 2 hours in a drying oven at the temperature of 110 ℃, and then heating the solution to 550 ℃ in an atmosphere of normal pressure air at the speed of 2 ℃/min and roasting the dried solution for 4 hours to obtain a calcined product, namely the 5 percent Cu-ZSM-5 catalyst.
2. Catalyst evaluation
Putting the prepared catalyst in a micro fixed bed quartz reactor, and introducing waste gas and O simulating the carbon fiber production process2(3 vol%) of mixed gas, the total flow is 100ml/min, and the airspeed of the mixed gas is 20000h-1The reaction temperature range is 200-600 ℃. On-line quantitative analysis of gas was carried out using a Nicolet Nexus 470 type infrared spectrometer with a 2.4m optical path gas analysis cell to obtain the conversion of each component and the yield of each reaction product in the waste gas from the carbon fiber production process. The conversion rate of 5 percent Cu-ZSM-5 catalyst on the catalytic combustion of a plurality of harmful components in the carbon fiber production process waste gas process and N are obtained by detection under the condition of different reaction temperatures2Yield (fig. 4). The optimum reaction temperature was found to be 350 ℃ by analysis, at which point the HCN conversion reached 100%, NH3The conversion rate reaches 99%, the CO conversion rate reaches 100%, and the yield of N2 reaches 97.30%.
[ example 2 ]
1. Catalyst preparation
A certain amount of copper nitrate (weighed according to the loading amount of 5% by mass of Cu) is dissolved in 200ml of deionized water to prepare a solution, and 2.0g of SiO is weighed2/A12O3Mixing the solution with an H-Beta molecular sieve of 30 ℃, fully stirring the mixture for 8 hours in a water bath kettle at the temperature of 40 ℃, slowly evaporating the water in the solution by using a rotary vacuum evaporator, drying the solution for 2 hours in a drying oven at the temperature of 110 ℃, and then heating the solution to 550 ℃ in an atmosphere of normal pressure air at the speed of 2 ℃/min and roasting the dried solution for 4 hours to obtain a calcined product, namely the 5% Cu-Beta catalyst.
2. Catalyst evaluation
Putting the prepared catalyst in a micro fixed bed quartz reactor, and introducing a certain amount of carbon fiber production process waste gas and O2(3 vol%) of mixed gas, the total flow is 100ml/min, and the airspeed of the mixed gas is 20000h-1The reaction temperature is 200-600 ℃. On-line quantitative analysis of gas was carried out using a Nicolet Nexus 470 type infrared spectrometer with a 2.4m optical path gas analysis cell to obtain the conversion of each component and the yield of each reaction product in the waste gas from the carbon fiber production process. The conversion rate of 5 percent of Cu-Beta catalyst on the catalytic combustion of various harmful components in the waste gas process of the carbon fiber production process and N are obtained by detection under the condition of different reaction temperatures2Yield (fig. 5). The optimum reaction temperature was found to be 500 ℃ by analysis, at which point the HCN conversion reached 100%, NH3The conversion rate reaches 99.04%, the CO conversion rate reaches 100%, and the yield of N2 reaches 89.14%.
[ example 3 ]
1. Catalyst preparation
A certain amount of copper nitrate (weighed according to the loading amount of 5% by mass of Cu) is dissolved in 200ml of deionized water to prepare a solution, and 2.0g of SiO is weighed2/Al2O3Mixing the solution with 30% H-ZSM-35 molecular sieve, stirring in 40 deg.C water bath for 8 hr, slowly evaporating water to dryness by rotary vacuum evaporator, drying in 110 deg.C oven for 2 hr, and heating at 2 deg.C/min in normal pressure air atmosphereAnd (3) roasting for 4 hours at the temperature of 550 ℃, and obtaining a calcined product, namely the 5% Cu-ZSM-35 catalyst.
2. Catalyst evaluation
Putting the prepared catalyst in a micro fixed bed quartz reactor, and introducing a certain amount of carbon fiber production process waste gas and O2(3 vol%) of mixed gas, the total flow is 100ml/min, and the airspeed of the mixed gas is 20000h-1The reaction temperature is 200-600 ℃. On-line quantitative analysis of gas was carried out using a Nicolet Nexus 470 type infrared spectrometer with a 2.4m optical path gas analysis cell to obtain the conversion of each component and the yield of each reaction product in the waste gas from the carbon fiber production process. The conversion rate of 5 percent Cu-ZSM-35 catalyst on the catalytic combustion of a plurality of harmful components in the carbon fiber production process waste gas process and N are obtained by detection under the condition of different reaction temperatures2Yield (fig. 5). The optimum reaction temperature was 450 ℃ by analysis, at which point the HCN conversion reached 100%, NH3The conversion rate reaches 99%, the CO conversion rate reaches 100%, and the yield of N2 reaches 92.22%.
[ example 4 ]
1. Catalyst preparation
A certain amount of copper nitrate (weighed according to the loading amount of 5% by mass of Cu) is dissolved in 200ml of deionized water to prepare a solution, and 2.0g of SiO is weighed2/Al2O3Mixing the solution with an H-Mor molecular sieve of 30 percent, fully stirring the mixture in a water bath kettle at the temperature of 40 ℃ for 8 hours, slowly evaporating the water in the solution by using a rotary vacuum evaporator, drying the solution in a drying oven at the temperature of 110 ℃ for 2 hours, and then heating the solution to 550 ℃ in an atmosphere of normal pressure air at the speed of 2 ℃/min to roast the solution for 4 hours to obtain a calcined product, namely the 5 percent Cu-Mor catalyst.
2. Catalyst evaluation
Putting the prepared catalyst in a micro fixed bed quartz reactor, and introducing a certain amount of carbon fiber production process waste gas and O2(3 vol%) of mixed gas, the total flow is 100ml/min, and the airspeed of the mixed gas is 20000h-1On-line quantitative analysis of gas is carried out by Nicolet Nexus 470 type infrared spectrometer with 2.4m optical path gas analysis cell, thus obtaining the components in the waste gas of carbon fiber production processConversion and yield of each reaction product. The conversion rate of 5 percent Cu-Mor catalyst to catalytic combustion of various harmful components in the waste gas process of the carbon fiber production process and N are obtained by detection under the condition of different reaction temperatures2Yield (fig. 5). The optimum reaction temperature was found to be 500 ℃ by analysis, at which point the HCN conversion reached 100%, NH3The conversion rate reaches 99.18%, the CO conversion rate reaches 100%, and the yield of N2 reaches 89.96%.
[ example 5 ]
1. Catalyst preparation
A certain amount of copper nitrate (weighed according to the loading amount of 5% by mass of Cu) is dissolved in 200ml of deionized water to prepare a solution, and 2.0g of SiO is weighed2/Al2O3Mixing the solution with a 30% H-MCM-22 molecular sieve, fully stirring for 8 hours in a 40 ℃ water bath, slowly evaporating the water in the solution by using a rotary vacuum evaporator, drying for 2 hours in a 110 ℃ oven, heating to 550 ℃ at the speed of 2 ℃/min in an atmosphere of normal pressure air, and roasting for 4 hours to obtain a calcined product, namely the 5% Cu-MCM-22 catalyst.
2. Catalyst evaluation
Putting the prepared catalyst in a micro fixed bed quartz reactor, and introducing a certain amount of carbon fiber production process waste gas and O2(3 vol%) of mixed gas, the total flow is 100ml/min, and the airspeed of the mixed gas is 20000h-1The reaction temperature is 200-600 ℃. On-line quantitative analysis of gas was carried out using a Nicolet Nexus 470 type infrared spectrometer with a 2.4m optical path gas analysis cell to obtain the conversion of each component and the yield of each reaction product in the waste gas from the carbon fiber production process. The conversion rate of 5 percent Cu-MCM-22 catalyst on the catalytic combustion of a plurality of harmful components in the carbon fiber production process waste gas process and N are obtained by detection under the condition of different reaction temperatures2Yield (fig. 5). The optimum reaction temperature was found to be 500 ℃ by analysis, at which point the HCN conversion reached 100%, NH3The conversion rate reaches 99.15 percent, the CO conversion rate reaches 100 percent, and the yield of N2 reaches 94.12 percent.
[ example 6 ]
1. Catalyst preparation
Taking a certain amount of copper nitrate (by mass)A load of 5% fractional Cu) was dissolved in 200ml of deionized water to prepare a solution, and 2.0g of SiO was weighed2/Al2O3Mixing the solution with a 30% H-MCM-49 molecular sieve, fully stirring for 8 hours in a 40 ℃ water bath, slowly evaporating the water in the solution by using a rotary vacuum evaporator, drying for 2 hours in a 110 ℃ oven, and then heating to 550 ℃ at the speed of 2 ℃/min in an atmosphere of normal pressure air to roast for 4 hours to obtain a calcined product, namely the 5% Cu-MCM-49 catalyst.
2. Catalyst evaluation
Putting the prepared catalyst in a micro fixed bed quartz reactor, and introducing a certain amount of carbon fiber production process waste gas and O2(3 vol%) of mixed gas, the total flow is 100ml/min, and the airspeed of the mixed gas is 20000h-1The reaction temperature is 200-600 ℃. On-line quantitative analysis of gas was carried out using a Nicolet Nexus 470 type infrared spectrometer with a 2.4m optical path gas analysis cell to obtain the conversion of each component and the yield of each reaction product in the waste gas from the carbon fiber production process. The conversion rate and N of 5 percent Cu-MCM-49 catalyst on the catalytic combustion of various harmful components in the carbon fiber production process waste gas process under different reaction temperature conditions are obtained through detection2Yield (fig. 5). The optimum reaction temperature was found to be 500 ℃ by analysis, at which point the HCN conversion reached 100%, NH3The conversion rate reaches 99.06%, the CO conversion rate reaches 100%, and the yield of N2 reaches 96.98%.
[ example 7 ]
1. Catalyst preparation
Dissolving a certain amount of cobalt nitrate (weighed according to the loading amount of Co with the mass fraction of 5%) in 200ml of deionized water to prepare a solution, weighing 2.0g of SiO2/Al2O3Mixing the solution with an H-ZSM-5 molecular sieve of 30 percent, fully stirring the mixture for 8 hours in a water bath kettle at the temperature of 40 ℃, slowly evaporating the water in the solution by using a rotary vacuum evaporator, drying the mixture for 2 hours in a drying oven at the temperature of 110 ℃, and then heating the mixture to 550 ℃ in an atmosphere of normal pressure air at the speed of 2 ℃/min and roasting the mixture for 4 hours to obtain a calcined product, namely the 5 percent Co-ZSM-5 catalyst.
2. Catalyst evaluation
Putting the prepared catalyst in a micro fixed bed quartz reactor, and introducing a certain amount of carbon fiber production process waste gas and O2(3 vol%) of mixed gas, the total flow is 100ml/min, and the airspeed of the mixed gas is 20000h-1The reaction temperature is 200-600 ℃. On-line quantitative analysis of gas was carried out using a Nicolet Nexus 470 type infrared spectrometer with a 2.4m optical path gas analysis cell to obtain the conversion of each component and the yield of each reaction product in the waste gas from the carbon fiber production process. The conversion rate of 5 percent Co-ZSM-5 catalyst on the catalytic combustion of a plurality of harmful components in the waste gas process of the carbon fiber production process and N are obtained by detection under the condition of different reaction temperatures2Yield (fig. 4). The optimum reaction temperature was found to be 400 ℃ by analysis, at which point the HCN conversion reached 100%, NH3The conversion rate reaches 99.63 percent, the CO conversion rate reaches 100 percent, and the yield of N2 reaches 48.79 percent.
[ example 8 ]
1. Catalyst preparation
Dissolving a certain amount of ferric nitrate (weighed according to the load amount of 5% Fe by mass) in 200ml of deionized water to prepare a solution, and weighing 2.0g of SiO2/Al2O3Mixing the solution with an H-ZSM-5 molecular sieve of 30 percent, fully stirring the mixture for 8 hours in a water bath kettle at the temperature of 40 ℃, slowly evaporating the water in the solution by using a rotary vacuum evaporator, drying the solution for 2 hours in a drying oven at the temperature of 110 ℃, and then heating the solution to 550 ℃ in an atmosphere of normal pressure air at the speed of 2 ℃/min and roasting the dried solution for 4 hours to obtain a calcined product, namely the 5 percent Fe-ZSM-5 catalyst.
2. Catalyst evaluation
Putting the prepared catalyst in a micro fixed bed quartz reactor, and introducing a certain amount of carbon fiber production process waste gas and O2(3 vol%) of mixed gas, the total flow is 100ml/min, and the airspeed of the mixed gas is 20000h-1The reaction temperature is 200-600 ℃. On-line quantitative analysis of gas was carried out using a Nicolet Nexus 470 type infrared spectrometer with a 2.4m optical path gas analysis cell to obtain the conversion of each component and the yield of each reaction product in the waste gas from the carbon fiber production process. The detection shows that the 5 percent Fe-ZSM-5 catalyst is used for carbon fiber production process waste gas under the condition of different reaction temperaturesConversion rate and N of catalytic combustion of various harmful components2Yield (fig. 4). The optimum reaction temperature was found by analysis to be 600 ℃ at which point the HCN conversion reached 100%, NH3The conversion rate reaches 98.2 percent, the CO conversion rate reaches 100 percent, and the yield of N2 reaches 92.20 percent.
[ example 9 ]
1. Catalyst preparation
Dissolving a certain amount of manganese nitrate (weighed according to the loading amount of 5% Mn by mass) in 200ml of deionized water to prepare a solution, weighing 2.0g of SiO2/Al2O3Mixing the solution with an H-ZSM-5 molecular sieve of 30 percent, fully stirring the mixture for 8 hours in a water bath kettle at the temperature of 40 ℃, slowly evaporating the water in the solution by using a rotary vacuum evaporator, drying the solution for 2 hours in a drying oven at the temperature of 110 ℃, and then heating the solution to 550 ℃ in an atmosphere of normal pressure air at the speed of 2 ℃/min and roasting the dried solution for 4 hours to obtain a calcined product, namely the 5 percent Mn-ZSM-5 catalyst.
2. Catalyst evaluation
Putting the prepared catalyst in a micro fixed bed quartz reactor, and introducing a certain amount of carbon fiber production process waste gas and O2(3 vol%) of mixed gas, the total flow is 100ml/min, and the airspeed of the mixed gas is 20000h-1The reaction temperature is 200-600 ℃. On-line quantitative analysis of gas was carried out using a Nicolet Nexus 470 type infrared spectrometer with a 2.4m optical path gas analysis cell to obtain the conversion of each component and the yield of each reaction product in the waste gas from the carbon fiber production process. The conversion rate of 5 percent Mn-ZSM-5 catalyst on the catalytic combustion of a plurality of harmful components in the waste gas process of the carbon fiber production process and N are obtained by detection under the condition of different reaction temperatures2Yield (fig. 4). The optimum reaction temperature was found to be 500 ℃ by analysis, at which point the HCN conversion reached 100%, NH3The conversion rate reaches 99.08 percent, the CO conversion rate reaches 100 percent, and the yield of N2 reaches 82.10 percent.
[ example 10 ]
1. Catalyst preparation
Dissolving a certain amount of nickel nitrate (weighed according to the load amount of 5% of Ni by mass) in 200ml of deionized water to prepare a solution, weighing 2.0g of SiO2/Al2O3＝30H-ZSM-5 molecular sieve is mixed with the solution, the mixture is fully stirred for 8 hours in a water bath kettle at the temperature of 40 ℃, the water in the solution is slowly evaporated by a rotary vacuum evaporator, the mixture is dried for 2 hours in a drying oven at the temperature of 110 ℃, and then the mixture is heated to 550 ℃ in the atmosphere of normal pressure air at the speed of 2 ℃/min and is roasted for 4 hours, and the obtained calcination product is the 5 percent Ni-ZSM-5 catalyst.
2. Catalyst evaluation
Putting the prepared catalyst in a micro fixed bed quartz reactor, and introducing a certain amount of carbon fiber production process waste gas and O2(3 vol%) of mixed gas, the total flow is 100ml/min, and the airspeed of the mixed gas is 20000h-1The reaction temperature is 200-600 ℃. On-line quantitative analysis of gas was carried out using a Nicolet Nexus 470 type infrared spectrometer with a 2.4m optical path gas analysis cell to obtain the conversion of each component and the yield of each reaction product in the waste gas from the carbon fiber production process. The conversion rate of 5 percent Ni-ZSM-5 catalyst on the catalytic combustion of a plurality of harmful components in the carbon fiber production process waste gas process and N are obtained by detection under the condition of different reaction temperatures2Yield (fig. 4). The optimum reaction temperature was found by analysis to be 600 ℃ at which point the HCN conversion reached 100%, NH3The conversion rate reaches 98.90 percent, the CO conversion rate reaches 100 percent, and the yield of N2 reaches 95.96 percent.
[ example 11 ]
1. Catalyst preparation
A certain amount of copper nitrate (weighed according to the loading amount of 5% by mass of Cu) is dissolved in 200ml of deionized water to prepare a solution, and 2.0g of SiO is weighed2/Al2O3Mixing the solution with 85% H-ZSM-5 molecular sieve, stirring in a 40 deg.C water bath for 8 hr, slowly evaporating water from the solution by using a rotary vacuum evaporator, drying in a 110 deg.C oven for 2 hr, heating to 550 deg.C at 2 deg.C/min in normal pressure air atmosphere, and calcining for 4 hr to obtain 5% Cu-ZSM-5 (SiO)2/Al2O385) catalyst.
2. Catalyst evaluation
Putting the prepared catalyst in a micro fixed bed quartz reactor, and introducing a certain amount of carbon fiber vitaminProcess off-gas and O2(3 vol%) of mixed gas, the total flow is 100ml/min, and the airspeed of the mixed gas is 20000h-1The reaction temperature is 200-600 ℃. On-line quantitative analysis of gas was carried out using a Nicolet Nexus 470 type infrared spectrometer with a 2.4m optical path gas analysis cell to obtain the conversion of each component and the yield of each reaction product in the waste gas from the carbon fiber production process. Detecting to obtain 5 percent Cu-ZSM-5 (SiO) under different reaction temperature conditions2/Al2O385) conversion rate of catalyst to catalytic combustion of various harmful components in waste gas process of carbon fiber production process and N2Yield (fig. 6). The optimum reaction temperature was found to be 500 ℃ by analysis, at which point the HCN conversion reached 100%, NH3The conversion rate reaches 99%, the CO conversion rate reaches 100%, and the yield of N2 reaches 91.40%.
[ example 12 ]
1. Catalyst preparation
A certain amount of copper nitrate (weighed according to the loading amount of 5% by mass of Cu) is dissolved in 200ml of deionized water to prepare a solution, and 2.0g of SiO is weighed2/Al2O3Mixing 150H-ZSM-5 molecular sieve with the solution, fully stirring the mixture in a water bath kettle at the temperature of 40 ℃ for 8 hours, slowly evaporating the water in the solution by using a rotary vacuum evaporator, drying the mixture in a drying oven at the temperature of 110 ℃ for 2 hours, heating the dried mixture to 550 ℃ in an atmosphere of normal pressure air at the speed of 2 ℃/min, and roasting the dried mixture for 4 hours to obtain a calcined product, namely 5% Cu-ZSM-5 (siO)2/Al2O3150) catalyst.
2. Catalyst evaluation
Putting the prepared catalyst in a micro fixed bed quartz reactor, and introducing a certain amount of carbon fiber production process waste gas and O2(3 vol%) of mixed gas, the total flow is 100ml/min, and the airspeed of the mixed gas is 20000h-1The reaction temperature is 200-600 ℃. On-line quantitative analysis of gas was carried out using a Nicolet Nexus 470 type infrared spectrometer with a 2.4m optical path gas analysis cell to obtain the conversion of each component and the yield of each reaction product in the waste gas from the carbon fiber production process. Detecting to obtain 5 percent Cu-ZSM-5 (SiO) under different reaction temperature conditions2/Al2O3150) conversion of catalyst to catalytic combustion of various harmful components of carbon fiber production process exhaust gas process and N2Yield (fig. 6). The optimum reaction temperature was found to be 550 ℃ when the HCN conversion reached 100%, NH3The conversion rate reaches 99.01 percent, the CO conversion rate reaches 63.55 percent, and the yield of N2 reaches 69.29 percent.
[ example 13 ]
1. Catalyst preparation
Dissolving a certain amount of copper nitrate (weighed according to the loading amount of 5% by mass of Cu) in 200ml of deionized water to prepare a solution, weighing 2.0g of Silicalite-1 molecular sieve, mixing with the solution, fully stirring for 8 hours in a 40 ℃ water bath kettle, slowly evaporating the water in the solution by using a rotary vacuum evaporator, drying for 2 hours in a 110 ℃ oven, heating to 550 ℃ at the speed of 2 ℃/min in an atmospheric air atmosphere, and roasting for 4 hours to obtain a calcined product, namely the 5% Cu-Silicalite-1 catalyst.
2. Catalyst evaluation
Putting the prepared catalyst in a micro fixed bed quartz reactor, and introducing a certain amount of carbon fiber production process waste gas and O2(3 vol%) of mixed gas, the total flow is 100ml/min, and the airspeed of the mixed gas is 20000h-1The reaction temperature is 200-600 ℃. On-line quantitative analysis of gas was carried out using a Nicolet Nexus 470 type infrared spectrometer with a 2.4m optical path gas analysis cell to obtain the conversion of each component and the yield of each reaction product in the waste gas from the carbon fiber production process. The conversion rate and N of 5 percent of Cu-Silicalite-1 catalyst on the catalytic combustion of various harmful components in the carbon fiber production process waste gas process under different reaction temperature conditions are obtained through detection2Yield (fig. 6). The optimum reaction temperature was found to be 400 ℃ by analysis, at which point the HCN conversion reached 100%, NH3The conversion rate reaches 99.22%, the CO conversion rate reaches 100%, and the yield of N2 reaches 56.94%.
[ example 14 ]
1. Catalyst preparation
A certain amount of copper nitrate (weighed according to the loading amount of 5 percent by mass of Cu) is dissolved in 200ml of deionized water to prepare a solution, 2.5g of pseudoboehmite is weighed,mixing with the solution, stirring in 40 deg.C water bath for 8 hr, slowly evaporating water in the solution by rotary vacuum evaporator, drying in 110 deg.C oven for 2 hr, heating to 550 deg.C at 2 deg.C/min in normal pressure air atmosphere, and calcining for 4 hr to obtain 5% Cu-Al calcined product2O3A catalyst.
2. Catalyst evaluation
Putting the prepared catalyst in a micro fixed bed quartz reactor, and introducing a certain amount of carbon fiber production process waste gas and O2(3 vol%) of mixed gas, the total flow is 100ml/min, and the airspeed of the mixed gas is 20000h-1The reaction temperature is 200-600 ℃. On-line quantitative analysis of gas was carried out using a Nicolet Nexus 470 type infrared spectrometer with a 2.4m optical path gas analysis cell to obtain the conversion of each component and the yield of each reaction product in the waste gas from the carbon fiber production process. The detection shows that 5 percent of Cu-Al is obtained under the conditions of different reaction temperatures2O3Conversion rate of catalyst to catalytic combustion of multiple harmful components in carbon fiber production process waste gas process and N2Yield (fig. 6). The optimum reaction temperature was found by analysis to be 600 ℃ at which point the HCN conversion reached 100%, NH3The conversion rate reaches 99.01 percent, the CO conversion rate reaches 100 percent, and the yield of N2 reaches 85.15 percent.
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| CN114849706A (en) | 2022-08-05 |
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Application publication date: 20220208 |