CN107983362B - Preparation method and utilization method of catalyst derived from waste - Google Patents
Preparation method and utilization method of catalyst derived from waste Download PDFInfo
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- CN107983362B CN107983362B CN201711235059.9A CN201711235059A CN107983362B CN 107983362 B CN107983362 B CN 107983362B CN 201711235059 A CN201711235059 A CN 201711235059A CN 107983362 B CN107983362 B CN 107983362B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 181
- 239000002699 waste material Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000197 pyrolysis Methods 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000000571 coke Substances 0.000 claims abstract description 32
- 239000010802 sludge Substances 0.000 claims abstract description 32
- 239000002028 Biomass Substances 0.000 claims abstract description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 23
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001447 ferric ion Inorganic materials 0.000 claims abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 86
- 239000003546 flue gas Substances 0.000 claims description 86
- 239000002245 particle Substances 0.000 claims description 36
- 239000003638 chemical reducing agent Substances 0.000 claims description 30
- 210000003608 fece Anatomy 0.000 claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- 239000010871 livestock manure Substances 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 239000002737 fuel gas Substances 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- 230000003213 activating effect Effects 0.000 claims description 21
- 238000002407 reforming Methods 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 19
- 241000264877 Hippospongia communis Species 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 238000005507 spraying Methods 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 238000002485 combustion reaction Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- 238000002309 gasification Methods 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 7
- 239000012047 saturated solution Substances 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000012258 stirred mixture Substances 0.000 claims description 4
- 239000010801 sewage sludge Substances 0.000 claims description 3
- 239000008188 pellet Substances 0.000 claims 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 abstract description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 239000010902 straw Substances 0.000 description 13
- 238000001994 activation Methods 0.000 description 11
- 230000004913 activation Effects 0.000 description 10
- 239000003814 drug Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000004566 building material Substances 0.000 description 7
- 239000000428 dust Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 235000017060 Arachis glabrata Nutrition 0.000 description 6
- 241001553178 Arachis glabrata Species 0.000 description 6
- 235000010777 Arachis hypogaea Nutrition 0.000 description 6
- 235000018262 Arachis monticola Nutrition 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 235000020232 peanut Nutrition 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 235000013399 edible fruits Nutrition 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000002920 hazardous waste Substances 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- 241001149258 Sporobolus alterniflorus Species 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011335 coal coke Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000011068 loading method Methods 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011271 tar pitch Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2067—Urea
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method for preparing and utilizing a waste-derived catalyst, which comprises the following steps: will be selected from KOH or K2CO3、Fe3+One or more of manganese nitrate and nickel nitrate are mixed into the sludge or biomass according to the proportion, the mixture is fully stirred, then the stirred sludge or biomass is subjected to anaerobic pyrolysis reaction at the temperature of 650-900 ℃, active coke is obtained in one step, and then the active coke is cleaned by clear water, dehydrated and dried to obtain the catalyst. The denitration efficiency of more than 80 percent can be obtained by using the catalyst powder or the molded product at the temperature of 100-360 ℃. The catalyst can promote tar cracking, and has no tar discharge and energy self-supply in the preparation process; no pollution after failure.
Description
Technical Field
The invention belongs to the technical field of harmless and resource treatment of wastes, and particularly relates to a preparation and utilization method of a waste-derived catalyst, which can produce the catalyst by utilizing sludge, pig manure, cow manure, medicine residues and agricultural and forestry wastes under the condition of not generating secondary pollution, and can not bring extra CO emission when the catalyst is utilized; the fuel gas can also be recovered after the catalyst is deactivated.
Background
The charcoal-based catalyst has wide application, can be applied to the treatment of wastewater containing heavy metals and organic pollutants difficult to degrade, for example, the patent application 'a biochar catalyst, an iron-carbon catalyst and application thereof' (CN 201610168376.2 application No. 2016.03.22) discloses the preparation and application of a biochar catalyst and an iron-carbon catalyst, wherein the biochar catalyst takes biochar as a carrier and loads rare earth metal oxide and Fe3O4(ii) a Preparing high-quality biochar in advance, and then loading nanoscale rare earth metal oxide and Fe on the biochar3O4Prepared to obtain the product which can be applied to organic pollution containing heavy metal and difficult to degradeThe catalyst in the wastewater treatment can obviously improve the wastewater treatment effect.
A resource method for changing sludge into things of value and utilizing sludge to manufacture a catalyst is reported in The literature, and The method for manufacturing sludge into activated coke in The prior art generally comprises The steps of firstly carrying out pyrolysis carbonization on sludge to obtain carbon, and then carrying out different activation methods such as a physical activation method, a chemical activation method and a physical-chemical combined activation method to achieve a better activation effect [ Kojima N, Mitomo A, Itaya Y, et al. Adsorption removal of polar by active keys produced from slag in The energy recovery process of Waste [ J ]. Waste management, 2002(22): 399-. However, the process of carbonization before activation is very complicated, and the activation effect can also change along with the change of different variables in the process; for processes employing physical activation, contacting Waste materials (e.g., sludge, pig manure, cow manure, biomass) with high temperature media such as steam, carbon dioxide, etc., after carbonization, consumes a large amount of energy [ Kojima N, Mitomo A, Itaya Y, et al, Adsorption removal of lipids by active drugs produced from slag in the energy processes of waters management, 2002(22) 399-404. Jundorc C, Meeyoo V, Kiyanan B, et al, Surface catalysis and dye Adsorption capacities of metals from slag adsorbed microorganisms/catalysis of solids recovery [ J ] Chemical Engineering, journal No. 133, journal No. 246; for the chemical activation process, charring the shell and sludge and then impregnating them with an activator also produces additional water pollution [ Jo Y B, Cha J S, Ko J H, Shin M S, Park S H, Jeon J K, Kim S, Park Y K, NH3 catalytic reduction (SCR) of nitrogen oxides (NOx) over activated water slurry channel Korean J Chem Eng 2011; 28: 106-113 Hwang H, Choi W, Kim T. the prediction of an adsorbed microorganisms of water slurry and co-tar pitch using an adsorbed water reaction [ J ] 2008. pyrolysis, 2008, 226 ]. The invention provides a preparation method of a catalyst by a one-step activation method, which comprises the following steps: directly adding an activator into wet sludge, pig manure and cow manure or other biomass wastes such as straw, fruit shell and herb residue powder, dissolving activator crystals by using water of the wet sludge, the pig manure and the cow manure to form an activator solution, and fully stirring; or other biomass is mixed with the saturated solution of the activating agent, and the biomass is fully impregnated; and further preparing active coke through an anaerobic pyrolysis reaction at the temperature of 650-900 ℃, and obtaining the catalyst after washing, dehydration and air drying. The invention can reduce the complexity of the working procedure, reduce the influence factor of the activation effect, save the energy and reduce the secondary pollution. The catalyst can be used for sewage treatment and toxic gas adsorption in the prior art, can also be used for flue gas denitration, and avoids the problem of CO release commonly encountered by active coke in the prior art in the flue gas denitration process. In addition, the catalyst can also be used for catalytic reforming of tar.
Disclosure of Invention
It is an object of the present invention to provide a process for the preparation and utilization of waste-derived catalysts.
The purpose of the invention is realized by the following method:
the invention provides a preparation method of a catalyst derived from waste, which comprises the following specific steps: mixing an activating agent into biomass in advance, fully stirring to obtain a mixture, drying the stirred mixture, and performing anaerobic pyrolysis reaction at the temperature of 650-900 ℃ to obtain active coke in one step; washing the obtained active coke with clear water, dehydrating and drying to obtain the catalyst; wherein: the mass ratio of the activating agent to the biomass is 1:5-1: 1.
In the invention, the activating agent is KOH or K2CO3One or more of 3-valent iron ions, manganese nitrate or nickel nitrate.
In the invention, the biomass is wet sludge, pig manure and cow manure or the saturated solution of the biomass is mixed with other biomass.
In the invention, the stirring is carried out for more than 0.5 h.
In the invention, the wet sludge is municipal sewage sludge or oil sludge; the biomass adopts any one of medicine dregs, various straws, fruit shells or wood chips, and the waste raw materials are all wastes.
In the invention, the catalyst is processed and formed into a granular shape or a honeycomb body.
According to the application method of the waste-derived catalyst obtained by the preparation method, the catalyst is placed in a reactor, and a hydrazine and urea composite reducing agent or a melamine reducing agent is used for reaction at the temperature of 100-360 ℃, so that the flue gas denitration efficiency of more than 80% can be obtained, and excessive CO can not be generated in the flue gas.
According to the application method of the waste-derived catalyst obtained by the preparation method, the catalyst powder is sprayed into a flue gas temperature section of 100-360 ℃, and a hydrazine and urea composite reducing agent or a melamine reducing agent is sprayed at the same time, so that the flue gas denitration efficiency of more than 80% can be obtained, and excessive CO can not be generated in the flue gas.
According to the application method of the waste-derived catalyst obtained by the preparation method, the catalyst particles are placed in a flue gas fluidized bed at 100-360 ℃, and a specially-made hydrazine and urea composite reducing agent or melamine reducing agent is sprayed, so that the flue gas denitration efficiency of more than 90% can be obtained, and excessive CO can not be generated in the flue gas.
According to the use method of the waste-derived catalyst obtained by the preparation method, the catalyst is placed in a reactor, and flue gas at the temperature of 100-360 ℃ passes through the reactor, so that the flue gas denitration efficiency of more than 80% can be obtained, and excessive CO is not generated in the flue gas.
According to the application method of the waste-derived catalyst obtained by the preparation method, the catalyst powder is sprayed into a flue gas temperature section of 100-360 ℃, so that the flue gas denitration efficiency of more than 60% can be obtained, and excessive CO is not generated in the flue gas.
According to the use method of the waste-derived catalyst obtained by the preparation method, the catalyst particles are placed in a flue gas fluidized bed at 100-360 ℃, so that the flue gas denitration efficiency of more than 80% can be obtained, and excessive CO is not generated in the flue gas.
The method for using the waste-derived catalyst obtained by the preparation method provided by the invention comprises the steps of placing the catalyst in a reforming reactor, passing volatile components generated in the pyrolysis reaction process through the reforming reactor at the temperature of 600-800 ℃, and decomposing more than 99% of tar in the volatile components to obtain combustible gas.
According to the use method of the waste-derived catalyst obtained by the preparation method, the deactivated catalyst after the catalyst is utilized is placed in a gasification reactor, air or oxygen is introduced at the reaction temperature of 600-800 ℃, the catalyst is catalyzed and gasified, tar-free fuel gas is obtained, and the condition that the deactivated catalyst pollutes the environment is avoided.
In the present invention, the patent application number of the special hydrazine & urea composite reducing agent is CN 201210166529.1.
The application method of the waste-derived catalyst obtained by the preparation method provided by the invention comprises the steps of preparing the catalyst into particles or a honeycomb body, placing the particles or the honeycomb body in a reactor, and allowing flue gas at the temperature of 100-360 ℃ to pass through, wherein the superficial velocity is 1200--1The denitration efficiency of the flue gas can be more than 80 percent, and excessive CO can not be generated in the flue gas.
The method for using the waste-derived catalyst obtained by the preparation method provided by the invention comprises the step of spraying the catalyst into a flue gas temperature section of 100-360 ℃ in a powdery manner, wherein the concentration of the catalyst is 1.5g/m3Or more, the flue gas denitration efficiency of more than 60 percent can be obtained without generating excessive CO in the flue gas.
According to the use method of the waste-derived catalyst obtained by the preparation method, the catalyst is prepared into particles and placed in a flue gas fluidized bed at 100-360 ℃, so that the flue gas denitration efficiency of more than 80% can be obtained, and excessive CO is not generated in the flue gas.
In a preferred embodiment of the process of the invention, a combination of:
1. the method for using the catalyst derived from waste is characterized in that the catalyst is made into particles or a honeycomb body and placed in a reforming reactor, volatile components generated by pyrolysis reaction in the preparation process of the catalyst pass through the reforming reactor at the temperature of 600-800 ℃, and more than 99% of tar in the volatile components is decomposed to obtain combustible gas.
2. A method for preparing the waste-derived catalyst, characterized in that: the combustible gas can be used for combustion to supply heat energy required by the oxygen-free pyrolysis reaction and drying in the catalyst preparation process;
3. a method for utilizing the waste-derived catalyst, characterized by: after the catalyst is utilized, the inactivated catalyst can be placed in a gasification reactor, air or oxygen is introduced at the reaction temperature of 600-800 ℃, the inactivated catalyst is catalyzed and gasified, and the obtained tar-free fuel gas is further utilized, so that the inactivated catalyst does not need to be disposed as dangerous waste as the inactivated catalyst in the prior art, and the cost and the disposal site are saved.
In the process of the invention, it is preferred that the ratio of the activating agent to the waste material is activating agent: the dry mass of the waste material (sludge, pig manure, cow manure or other biomass) = mass ratio of 1:5 to 1: 1.
When the method is specifically implemented, the activating agent can be directly and fully mixed with the sludge, the pig manure and the cow manure and then stirred; or preparing the activating agent and water into saturated solution, and then soaking the medicine dregs, various straws, fruit shells and wood chips; forming a uniform mixture, drying and then feeding the mixture into an oxygen-free pyrolysis reactor to facilitate the preparation of active coke.
In the method, when the obtained active coke is washed by water, only ash and salt in the active coke are washed, and heavy metal and harmful organic matters are not contained in the washed water.
An embodiment of the invention for preparing a specific catalyst comprises the following steps:
(1) process for preparing catalyst from waste, KOH or K2CO33-valent iron ion (Fe)3+) One or more of manganese nitrate and nickel nitrate as an activator: the waste raw materials are in a mass ratio of 1:5-1:1Mixing the biomass with wet sludge, pig manure and cow manure in advance or mixing the biomass with a saturated solution of the wet sludge, the pig manure and the cow manure, and fully stirring for 0.5h or more by using the existing stirring technology such as a stirrer and the like to obtain a uniform mixture;
(2) drying the uniform mixture obtained after stirring, and then carrying out anaerobic pyrolysis reaction at the temperature of 650-900 ℃ to obtain active coke in one step;
(3) and (3) cleaning the active coke with clear water, dehydrating and drying to obtain the catalyst.
(4) The catalyst obtained in step (3) can be processed again into granules or honeycombs according to the requirements of the application by using the prior art.
Utilization embodiments of specific catalysts of the present invention include the following:
(1) the use method of the waste-derived catalyst comprises the steps of placing the catalyst particles or the honeycomb body in a reactor, and reacting at the temperature of 100-360 ℃ by using a specially-made hydrazine and urea composite reducing agent or a melamine reducing agent to obtain the flue gas denitration efficiency of more than 80% and avoid CO generation.
(2) The use method of the waste-derived catalyst comprises the steps of spraying the catalyst powder into a flue gas temperature section of 100-360 ℃, and simultaneously spraying a specially-prepared hydrazine and urea composite reducing agent or a melamine reducing agent, so that the flue gas denitration efficiency of more than 80% is obtained, and CO is prevented from being generated.
(3) The use method of the waste-derived catalyst comprises the steps of placing the catalyst particles in a flue gas fluidized bed at 100-360 ℃, and spraying a specially-made hydrazine and urea composite reducing agent or melamine reducing agent, so that the flue gas denitration efficiency is over 92 percent, and CO is avoided.
(4) The use method of the waste-derived catalyst comprises the steps of placing the catalyst particles or the honeycomb body in a reactor, allowing flue gas at the temperature of 100-360 ℃ to pass through, and not using a reducing agent, so that the flue gas denitration efficiency of more than 80% is obtained, and excessive CO is avoided.
(5) The use method of the waste-derived catalyst comprises the steps of spraying the catalyst powder into a flue gas temperature section of 100-360 ℃, and using no reducing agent, so that the flue gas denitration efficiency of more than 80% is obtained, and excessive CO is avoided.
(6) The use method of the waste-derived catalyst is that the catalyst particles are placed in a flue gas fluidized bed at 100-360 ℃, a reducing agent is not used, the flue gas denitration efficiency of more than 80% is obtained, and excessive CO is avoided.
The above 6 utilization methods can be preferably combined with the following 3 supplementary methods to achieve higher energy utilization efficiency and more environmental protection effects:
(1) and (3) placing the catalyst particles or the honeycomb body in a reforming reactor, and passing volatile components generated in the pyrolysis reaction process through the reforming reactor at the temperature of 600-800 ℃, wherein more than 99% of tar in the volatile components is decomposed to obtain combustible gas.
(2) Supplying heat energy required for the anaerobic pyrolysis reaction and drying in the step (2) of preparing the catalyst by using the combustion of the combustible gas;
(3) after the catalyst derived from the wastes is utilized and deactivated, the catalyst is placed in a gasification reactor, air or oxygen is introduced at the reaction temperature of 600-800 ℃, the catalyst is catalyzed and gasified, tar-free fuel gas is obtained, and the final disposal modes such as landfill and the like are avoided.
In the process of the invention, the terms have the following meanings:
the waste raw materials are carbon-containing raw materials including sewage sludge, oil sludge, pig manure, cow manure, various straws, fruit shells, wood chips, medicine residues and the like.
The anaerobic pyrolysis reaction refers to heating the waste raw materials to high temperature (the invention preferably adopts 650-900 ℃) under the condition of no oxygen supply to decompose the raw materials into volatile components and coke; wherein the volatile matter is a mixture of tar and combustible gas.
The drying is to heat the solid by using heat energy to evaporate the moisture in the solid at a temperature of not higher than 105 ℃; the dehydration and airing are carried out at normal temperature.
The deactivation means that the catalyst does not have the reactivity in a fresh state (before being used) after being used.
The 3-valent iron ion (Fe)3+) Is made into a fingerThe valence state is ferric ion, and comes from various soluble ferric salts, such as ferric nitrate, ferric sulfate, ferric oxide, etc.
The clear water can be industrial soft water, natural river water, other fresh water and tap water which is not disinfected by chlorine.
The method has the following beneficial effects:
1) in the method, the waste is utilized, the use of expensive activated carbon substrates is avoided, the preparation cost of the catalyst is reduced, and the efficient disposal of the waste is realized.
2) In the method, the active coke is obtained in one step by premixing the activating agent and the waste raw material and then performing anaerobic pyrolysis; the problems of long steps, high energy consumption, secondary pollution risk and the like existing in the prior art in the modes of firstly preparing carbon and then activating are solved.
3) In the method, the heat energy required by the preparation of fuel gas can be obtained by utilizing the volatile component generated in the reforming preparation process of the self-prepared catalyst, so that the energy cost is saved;
4) in the method, the deactivated catalyst can be used for self-catalytic gasification to recover fuel gas, thereby not only thoroughly disposing the waste, but also avoiding secondary pollution, not polluting the environment and avoiding becoming dangerous waste, which can not be realized in the prior art.
Detailed Description
The embodiments and effects of the present invention will be described in detail below with reference to specific examples.
Example 1
A batch of dewatered municipal sludge with water content of about 78% and dry-basis low-grade heat value of about 14 MJ/kg; if incineration disposal is adopted, supplementary energy is needed. Directly mixing KOH into sludge with water content of 78% according to the weight ratio of KOH to dry basis =1:1, stirring for 35min by a stirrer, drying to water content of below 25%, feeding into an anaerobic pyrolysis reactor, heating to 650 ℃ for anaerobic pyrolysis reaction to obtain active coke in one step, washing by clear water, dehydrating and airing, wherein the obtained catalyst contains rich oxygen-containing functional groups and has specific surface area of 178.53 m2(g) mesoporous volume 0.161cm3(vi)/g, most preferablyThe aperture of several pores is 1.85nm, and the activity is very good.
The catalyst is made into particles with the diameter of 4mm and the length of 5-6 mm by a double-screw extrusion granulator in the prior art, the particles are placed in a reforming reactor, the reforming reactor is connected behind an anaerobic pyrolysis reactor, volatile matters generated by the anaerobic pyrolysis reactor are introduced into the reforming reactor to be reformed at 800 ℃, more than 99% of tar is decomposed into fuel gas, high-temperature flue gas generated by combustion of the fuel gas is fed into the anaerobic pyrolysis reactor to supply heat, and the fuel gas is fed into a dryer to continue to supply heat after being cooled.
Putting the catalyst particles reacted in the reforming reactor into a denitration reactor, introducing flue gas at 360 ℃, and when the oxygen concentration in the flue gas is 6.5-8.5%, and the empty tower speed of the flue gas passing through a catalyst bed layer is 1200h-1When the denitration efficiency is 89-82%, the CO generated is less than 10mg/Nm3. After 1500 h operation, the denitration efficiency is obviously reduced, the inactivated catalyst is gasified by introducing pure oxygen at 600 ℃, tar-free combustible gas is obtained, and a small amount of residual ash can be used as building materials.
The ministry of environmental protection officials formally issued a notification about the supervision work of strengthening the waste flue gas denitration catalyst in 2014 8, incorporated the waste flue gas denitration catalyst (vanadium-titanium system) into hazardous waste for management, and classified the waste flue gas denitration catalyst into 'HW 49 other waste' in the national hazardous waste records; for hazardous waste, a country makes a lot of regulatory laws and regulations, and strict regulations are made on storage, packaging, transportation, disposal and the like of the hazardous waste, so that the disposal cost is high. The catalyst of the embodiment has no heavy metal, does not belong to hazardous waste after being discarded, and only leaves a small amount of ash which can be used as building materials after gasifying and recycling fuel gas, thereby completely avoiding the post-treatment procedure of using the vanadium-titanium denitration catalyst in factories in the prior art.
Example 2
A batch of oil sludge with the water content of about 70 percent and the dry-basis low calorific value of about 21 MJ/kg; if incineration disposal is adopted, higher flue gas purification investment is needed. Mixing the prepared saturated Fe (NO)3)3And Mn (NO)3)2Solution (control of Fe)3+/Mn2+1: 0.5) into the oil sludge with the water content of about 70 percent, and controlling Fe (NO)3)3And Mn (NO)3)2The mass ratio of the sum of the crystal mass and the dry oil sludge is 1:1, the mixture is fully stirred for 45min by a stirrer, then the mixture is dried until the water content is below 18 percent, the mixture is sent into an anaerobic pyrolysis reactor, the mixture is heated to 900 ℃ for anaerobic pyrolysis reaction, active coke is obtained in one step, the mixture is washed by clear water until the pH value is about 7, the mixture is dehydrated and dried, the obtained catalyst has rich oxygen-containing functional groups, and the specific surface area reaches 380.9m2(g) mesoporous volume 0.275cm3Per g, the most probable pore diameter is 1.90nm, and the activity is very good. The volatile components produced by the oxygen-free pyrolysis reactor contain a certain amount of nitrogen-containing compounds, and are directly combusted by adopting a low-nitrogen combustion technology similar to that disclosed in the patent CN201520063198.8, and high-temperature flue gas is generated to supply the heat energy required by the oxygen-free pyrolysis reactor and the heat energy required by drying.
The catalyst is made into a honeycomb body by using a forming machine in the prior art, the honeycomb body is placed in a denitration reactor, flue gas with the temperature of about 350 ℃ is introduced, and the ratio of the reducing agent to NOx is 1.05:1 spraying in hydrazine&The urea composite reducing agent has the advantages that when the oxygen concentration in the flue gas is 8-11 percent, the empty tower speed of the flue gas passing through the catalyst bed layer is 4600 h-1And in addition, the denitration efficiency reaches 83-90%. CO production less than 10mg/Nm3. After 2500 h of operation and deactivation, the catalyst is gasified by introducing air at 800 ℃ to obtain combustible gas without tar, and Mn in residual ash can be recovered by nitric acid.
And (3) economic analysis: the disposal cost of 1 ton of oil sludge in the prior art is about 1800-3000 yuan. By adopting the technology of the invention, from the perspective of an owner, the consumption of the reagents iron nitrate and manganese nitrate 50% solution in the production process is about 3500 yuan/ton, the consumption cost of the reagents for treating 1 ton of oil sludge is about 850 yuan, the energy in the production process is completely supplied by volatile and gas combustion, the yield of the catalyst is about 270 kg/ton of oil sludge, the selling price of the catalyst is about 16-20 yuan/kg according to the equivalent use price of the domestic catalyst in the prior art, the income is about 4320-.
Example 3
The water content of a batch of reed straws is about 25 percent, and the dry-basis low-grade heat value is about 15 MJ/kg; if the maximum selling price of combustion power generation is about 450 yuan/ton, farmers have no enthusiasm due to high harvesting cost and transportation cost. The prepared Fe (NO) is crushed by the technology of the invention to ensure that the granularity is less than 15mm3)3And Ni (NO)3)2Solution (control of Fe)3+/Ni2+The mol ratio is 1: 0.6) is evenly sprayed into the straw powder with the water content of about 25 percent, and Fe (NO) is controlled3)3And Ni (NO)3)2The mass ratio of the sum of the crystal mass and the dry straw is 1:5, the mixture is fully stirred for 45min by a stirrer, then the mixture is dried until the water content is below 18 percent, the mixture is sent into an anaerobic pyrolysis reactor, the mixture is heated to 800 ℃ for anaerobic pyrolysis reaction, active coke is obtained in one step, the mixture is washed by clear water until the pH value is about 7, the mixture is dehydrated and dried, the obtained catalyst has rich oxygen-containing functional groups, and the specific surface area reaches 459m2G, mesoporous volume 0.381cm3Per g, the most probable pore diameter is 1.97nm, and the activity is very good. The volatile components produced by the oxygen-free pyrolysis reactor contain a certain amount of nitrogen-containing compounds, and are directly combusted by adopting a low-nitrogen combustion technology similar to that disclosed in the patent CN201520063198.8, and high-temperature flue gas is generated to supply the heat energy required by the oxygen-free pyrolysis reactor and the heat energy required by drying.
The catalyst is prepared into particles by using a forming machine in the prior art, the particles are placed in a denitration reactor, flue gas with the temperature of about 150 ℃ is introduced, and the molar ratio of a reducing agent to NOx is 1.05:1 spraying in hydrazine&The urea composite reducing agent has the advantages that when the oxygen concentration in the flue gas is 8-11 percent, the empty tower speed of the flue gas passing through the catalyst bed layer is 3500h-1When the method is used, the denitration efficiency reaches 87-81%. After the catalyst is deactivated after 3000 hr operation, air is introduced into the catalyst at 800 deg.c to gasify to obtain tar-free combustible gas, and the Ni in the residual ash may be recovered with nitric acid.
And (3) economic analysis: the method has the advantages that the consumed medicament nickel nitrate is about 20000 yuan/ton, the iron nitrate is about 3500 yuan/ton, the medicament consumption cost for treating 1 ton of straws is about 2118 yuan, the energy in the production process is completely supplied by volatile components and fuel gas, the yield of the catalyst is about 260 kg/ton, the price is about 20-26 yuan/kg according to the equivalent use price of the domestic catalyst in the prior art, the income can be about 5200 and 6760 yuan/ton, the medicament cost is deducted, good benefits can be realized, and the straws are collected and transported by farmers with enthusiasm.
Example 4
The water content of a batch of spartina alterniflora straws is about 25 percent, and the dry-base low-grade heat value is about 15 MJ/kg; there is no suitable use. Pulverizing the iron oxide powder to make its granularity less than 5mm by said invented technology and making the iron oxide powder (Fe)2O3) Adding into saturated KOH solution (molar ratio 1: 1), stirring, spraying onto the above stalk powder with water content of about 25%, and controlling Fe2O3The mass ratio of KOH to dry straw is 1:2, stirring for 40min with a stirrer, drying to water content below 18%, feeding into an anaerobic pyrolysis reactor, heating to 800 ℃ for anaerobic pyrolysis reaction to obtain active coke in one step, washing with clear water to pH of about 7, dehydrating and drying to obtain a catalyst with rich oxygen-containing functional groups and specific surface area of 335m2Per g, mesoporous volume 0.277cm3Per g, the most probable pore diameter is 1.86nm, and the activity is very good. The catalyst is made into particles with the diameter of 4mm and the length of 5-6 mm by a forming machine in the prior art, the particles are placed in a fluidized bed denitration reactor, 100 ℃ flue gas is introduced, and when the oxygen concentration in the flue gas is 6.5-9%, the denitration efficiency is 91-81%, CO is not generated. The broken catalyst powder is collected by cyclone and bag-type dust collector, and is processed into particles again, part of the particles returns to the fluidized bed, and part of the particles is sent to the gasification furnace for gasification, and a small amount of ash residue remained after gasification can be used as building materials.
The volatile components produced by the anaerobic pyrolysis of the spartina alterniflora stalks can be catalytically reformed by the catalyst, and the fuel gas quantity obtained after 1 ton of spartina alterniflora anaerobic pyrolysis and catalytic reforming is about 430 m3Ton, 50% of which is sufficient for heating the oxygen-free pyrolysis reactor. The other 50% can be used for internal combustion engine to generate electricity, and each m3The gas energy can generate electricity by 1.5 degrees, and the redundant fuel gas of each ton of spartina alterniflora straws after the catalyst is produced can generate electricity by 325 degrees.
Example 5
Moisture content of a batch of peanut shellsAbout 10 percent, and the dry-based low calorific value is about 16 MJ/kg; firstly, crushing the mixture by a crusher until the granularity is less than 5 mm. Adding iron oxide powder to K2CO3In saturated solution (Fe/K molar ratio 2:1) according to (K)2CO3And ferric oxide) is added into the peanut shell powder according to the weight sum of dry peanut shell weight =1:3, the mixture is fully stirred for 35min by a stirrer, then the mixture is dried until the water content is below 25%, the mixture is sent into an anaerobic pyrolysis reactor, the anaerobic pyrolysis reaction is carried out after the mixture is heated to 800 ℃, active coke is obtained in one step, the active coke is washed by clean water and dehydrated and dried, the obtained catalyst has rich oxygen-containing functional groups, and the specific surface area reaches 398.7 m2(g) mesoporous volume 0.314 cm3Per g, the most probable pore diameter is 2.09nm, and the activity is very good.
The catalyst is made into particles with the diameter of 5mm and the length of 6-8 mm by a double-screw extrusion granulator in the prior art, the particles are placed in a reforming reactor, the reforming reactor is connected behind an anaerobic pyrolysis reactor, volatile components generated by the anaerobic pyrolysis reactor are introduced into the reforming reactor and reformed at the temperature of 800 ℃, 100 percent of tar is decomposed into fuel gas, high-temperature flue gas generated by combustion of the fuel gas is fed into the anaerobic pyrolysis reactor for heat supply, and the fuel gas is fed into a dryer for continuous heat supply after being cooled.
Putting the catalyst particles reacted in the reforming reactor into a fluidized bed denitration reactor, introducing flue gas at 360 ℃, and generating CO of less than 10mg/Nm when the oxygen concentration in the flue gas is 6.5-8.5 percent and the denitration efficiency is 91-83 percent3. The broken catalyst is collected by cyclone dust removal and bag-type dust remover during operation, and is processed into particles again, one part of the particles is sent into the fluidized bed reactor, the other part of the particles is gasified by air at 800 ℃ to obtain fuel gas, and a small amount of residual ash can be used as building materials.
The fuel gas quantity obtained after the volatile components generated by the anaerobic pyrolysis of the peanut shells are catalytically reformed by a catalyst is about 470 m3Ton, 49% of which is sufficient for heating the oxygen-free pyrolysis reactor. In addition, 51% of the power can be generated by the internal combustion engine, and the power can be generated every m3The gas energy can generate electricity by 1.7 degrees, and the surplus fuel gas generated after the catalyst is produced in each ton of peanut shells can generate more than 400 degrees of electricity.
Example 6
The catalyst prepared from peanut shells in example 5 above was washed, dried, and then mechanically processed into a honeycomb body; then placing the flue gas into a denitration reactor, introducing flue gas at about 150 ℃, spraying a melamine solution into the reactor as a reducing agent according to the quantity ratio of the reducing agent to NOx of 1:1, and when the oxygen concentration in the flue gas is 8-11 percent, the empty tower speed of the flue gas passing through a catalyst bed layer is 3600h-1When the process is carried out, the denitration efficiency is 88-91 percent, and CO is not generated. After 3000 h operation, the denitration efficiency is obviously reduced, the inactivated catalyst is gasified by introducing oxygen-enriched air at 700 ℃ to obtain combustible gas without tar, and a small amount of residual ash can be used as building materials.
Example 7
The water content of a batch of dregs is about 73 percent, the lower calorific value of a dry basis is about 16MJ/kg, and the dregs are regulated to be treated as dangerous waste. Mixing KOH solution and iron oxide powder, then directly mixing the KOH solution and the iron oxide powder into medicine dregs with the water content of 73 percent according to the mass sum of (KOH + iron oxide) and the mass of dry basis =1:2, fully stirring the mixture for 35min by using a stirrer, then drying the mixture until the water content is below 25 percent, feeding the mixture into an oxygen-free pyrolysis reactor, heating the mixture to 800 ℃ for oxygen-free pyrolysis reaction to obtain active coke in one step, washing the active coke by using clear water, dehydrating and airing the active coke, wherein the obtained catalyst contains rich oxygen-containing functional groups and has the specific surface area of 305.3 m2G, mesoporous volume 0.269cm3Per g, the most probable pore diameter is 2.35nm, and the activity is very good.
Making the catalyst into particles with a diameter of 4mm and a length of 6 mm by using a double-screw extrusion granulator in the prior art, placing the particles into a denitration reactor, and introducing 100-160 ℃ flue gas, wherein when the oxygen concentration in the flue gas is 9.5 percent, the empty tower speed of the flue gas passing through a catalyst bed layer is 1200h-1When the process is carried out, the denitration efficiency is 85-89%, and CO is not generated. After running for 1000 h, the denitration efficiency is obviously reduced, and pure N is introduced into the inactivated catalyst at the temperature of 600 DEG C2The gas is regenerated and can be reused. The finally invalid catalyst can be gasified by introducing pure oxygen at 600 ℃ to obtain tar-free combustible gas, and a small amount of residual ash can be used as building materials.
Example 8
A batch of cow dung with water content of about 81 percent and dry-basis low calorific value of 13.9MJ/kg. Directly mixing KOH and ferric oxide into the medicine dregs with water content of 81% according to the mass ratio of dry basis mass =1:5 and 1:4 respectively, fully stirring for 50min by using a stirrer, then drying to the water content of below 25%, feeding into an anaerobic pyrolysis reactor, heating to 800 ℃ for anaerobic pyrolysis reaction to obtain active coke in one step, washing by using clear water, dehydrating and drying in the air, wherein the obtained catalyst contains rich oxygen-containing functional groups and has specific surface area of 408.53 m2(g) mesoporous volume 0.301cm3Per g, the most probable pore diameter is 2.08nm, and the activity is very good.
The catalyst is made into a honeycomb body with a pore passage of 4mm by an extrusion molding machine in the prior art, the honeycomb body is placed in a denitration reactor, and flue gas with the temperature of 360 ℃ is introduced, when the oxygen concentration in the flue gas is 6.5-8.5 percent, and the empty tower speed of the flue gas passing through a catalyst bed layer is 4200h-1When the denitration efficiency is 90-82%, the CO generated is less than 10mg/Nm3CO produced by using coal coke as catalyst under the same condition is higher than 60mg/Nm3. The surface ash is swept by steam every 24 h in the operation process, the catalyst is deactivated after 3600h of operation, oxygen-enriched air is introduced for gasification at 750 ℃, tar-free combustible gas is obtained, and a small amount of residual ash can be used as building materials.
Example 9
The dry-base low-grade calorific value of a batch of pig manure (non-water-soaked manure) with the water content of about 70 percent is about 12.6 MJ/kg. Will K2CO3Mixing the solution and ferric oxide (K/Fe molar ratio =1:3), mixing the solution and ferric oxide into pig manure with water content of 70% according to the total mass of the two, namely dry basis mass =1:5, fully stirring for 45min, then drying to water content of below 25%, feeding into an anaerobic pyrolysis reactor, heating to 809 ℃ for anaerobic pyrolysis reaction to obtain active coke in one step, washing with clear water, dehydrating and airing, wherein the obtained catalyst contains rich oxygen-containing functional groups and has specific surface area of 408.53 m2G, mesoporous volume 0.331cm3Per g, the most probable pore diameter is 1.88nm, and the activity is very good.
The catalyst powder is directly sprayed into the flue gas at 350 ℃, a special reactor is not needed, and the spraying amount is 1.8g/Nm3When the oxygen concentration in the flue gas is 6.5-8.5%, the denitration efficiency is 75-69%; CO production less than 10mg/Nm3CO produced by using coal coke as catalyst under the same condition is higher than 60mg/Nm3. In the operation process, catalyst powder is collected by a bag-type dust collector, and part of the catalyst powder can be repeatedly sprayed into the bag-type dust collector for use; and part of the gas is discharged and gasified to recover the fuel gas.
Example 10
The catalyst powder described in example 9 above can also be sprayed directly into flue gas at about 260 ℃ without the need for a specially made reactor, at a spray rate of 1.5g/Nm3At the same time spraying special hydrazine into the flue gas&The injection amount of the urea reducing agent is that the equivalent ratio of the reducing agent to NOx is 1.05:1, and when the oxygen concentration in the flue gas is 8-11%, the denitration efficiency is 75-80%, and CO is not generated. In the operation process, catalyst powder is collected by a bag-type dust collector, and 60 percent of the catalyst powder can be repeatedly sprayed into the bag-type dust collector for use; 40% of the gas is discharged and gasified to recover the fuel gas.
Example 11
A batch of sawdust with water content of about 25% and dry-basis low calorific value of about 14.6 MJ/kg. Mixing KOH solution and ferric oxide (K/Fe molar ratio =1:2), uniformly spraying the mixture into wood chips according to the total mass of the two, namely the dry mass of the wood chips =1:4, fully stirring for 45min, then drying to the water content of below 25%, feeding the mixture into an anaerobic pyrolysis reactor, heating to 850 ℃ for anaerobic pyrolysis reaction to obtain active coke in one step, washing with clear water, dehydrating and airing, wherein the obtained catalyst contains rich oxygen-containing functional groups and has a specific surface area of 391.3 m2(g) mesoporous volume 0.334cm3Per g, the most probable pore diameter is 2.19nm, and the activity is very good. Processing the catalyst into particles by an extrusion molding machine, placing the particles into a denitration reactor, and spraying special hydrazine into flue gas&Urea reducing agent is sprayed in an amount that the equivalent ratio of the reducing agent to NOx is 1.05:1, and the superficial velocity of the flue gas passing through the catalyst at 170 ℃ is 4600 h-1When the oxygen concentration is 8-11%, the denitration efficiency is 80-85%, and CO is not generated. The catalyst after 2800 h was used to recover fuel gas by air gasification at 800 ℃.
The above examples show that: the method can be used for recovering sludge and waste biomass (dregs, various straws, fruit shells, pig manure and cow manure) and activating the sludge and the waste biomass in one step to obtain the catalyst, can be used for various denitration situations and can be used for catalyzing tar to be converted into fuel gas.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (9)
1. The use method of the catalyst derived from waste is characterized by comprising the following specific steps:
1) preparation step of catalyst
i) Will be selected from KOH or K2CO3The saturated solution and ferric oxide are mixed according to the molar ratio of K/Fe of 1:1-1:3 to be used as an activating agent, the two are mixed into the biomass waste after being stirred uniformly, the mixture is obtained by fully stirring, then the stirred mixture is dried and is subjected to anaerobic pyrolysis reaction at about 800 ℃, and active coke is obtained in one step; washing the obtained active coke with clear water, dehydrating and drying to obtain the catalyst; wherein, the activating agent: the mass ratio of the dry biomass waste is 1:5-1: 1;
or:
i) mixing an activator KOH and biomass waste into biomass in advance according to the dry mass of KOH: 1, fully stirring to obtain a mixture, drying the stirred mixture, and carrying out anaerobic pyrolysis reaction at 650 ℃ to obtain activated coke in one step; washing the obtained active coke with clear water, dehydrating and drying to obtain the catalyst; wherein: the mass ratio of the activating agent to the biomass is 1:5-1: 1;
ii) preparing the catalyst obtained in the step into particles, placing the particles into a reforming reactor, connecting the reforming reactor behind the oxygen-free pyrolysis reactor, and enabling volatile components generated in the pyrolysis reaction process to pass through the reforming reactor at 800 ℃ so as to decompose tar in the volatile components to obtain combustible gas;
the catalyst after reaction in the reforming reactor is a denitration catalyst;
alternatively, the first and second electrodes may be,
i) mixing Fe (NO)3)3Solution with Mn (NO)3)2Or Ni (NO)3)2Solution according to Fe3+/(Mn2+Or Ni2+) Mixing as an activating agent at a molar ratio of 1:0.5 or 1:0.6, mixing with the waste, stirring thoroughly with a stirrer, and then drying the stirred mixture; wherein, Fe (NO)3)3Solution with Mn (NO)3)2When the solution mixture is an activating agent, the mass ratio of the activating agent to the waste is 1: 1; fe (NO)3)3Solution with Ni (NO)3)2When the solution mixture is an activating agent, the mass ratio of the activating agent to the waste is 1: 5;
ii) to Fe (NO)3)3Solution with Mn (NO)3)2The dry waste obtained by using the solution mixture as an activating agent is subjected to anaerobic pyrolysis reaction at 900 ℃, or Fe (NO)3)3Solution with Ni (NO)3)2The solution mixture is taken as an activating agent to obtain dry waste, and the dry waste is subjected to anaerobic pyrolysis reaction at 800 ℃ to obtain active coke in one step; washing the obtained active coke with clear water, dehydrating and drying to obtain the catalyst;
2) step of utilizing catalyst
Placing the catalyst particles or the honeycomb body in a denitration reactor, and reacting at 100-360 ℃ by using a hydrazine and urea composite reducing agent or a melamine reducing agent to obtain the flue gas denitration efficiency of more than 80% without generating excessive CO in the flue gas;
alternatively, the first and second electrodes may be,
the catalyst is placed in a reactor, no reducing agent is used, and the flue gas at the temperature of 350--1The denitration efficiency of the flue gas of more than 80 percent can be obtained, and excessive CO can not be generated in the flue gas;
3) utilization step of deactivated catalyst
The inactivated catalyst is placed in a gasification reactor, air or oxygen is introduced at the reaction temperature of 600-800 ℃, the catalyst is catalyzed and gasified, tar-free fuel gas is obtained, useful elements in the catalyst are recovered, and the environment pollution caused by the inactivated catalyst is avoided.
2. The method of using a waste derived catalyst as claimed in claim 1, wherein: the biomass is wet sludge, pig manure and cow manure or the saturated solution of the biomass is mixed with other biomass.
3. Use of a waste derived catalyst according to claim 2, characterized in that: the wet sludge is municipal sewage sludge or oil sludge.
4. The method of using a waste derived catalyst as claimed in claim 1, wherein: the catalyst is powder.
5. The method of using a waste derived catalyst as claimed in claim 1, wherein: the catalyst is shaped into pellets or honeycombs.
6. The method of using a waste derived catalyst as claimed in claim 1, wherein: spraying the catalyst powder into a flue gas temperature section of 100-360 ℃; the concentration of which is 1.5g/m3Or more, the flue gas denitration efficiency of more than 60 percent can be obtained without generating excessive CO in the flue gas.
7. The method of using a waste derived catalyst as claimed in claim 1, wherein: the catalyst particles are placed in a flue gas fluidized bed at 100-360 ℃.
8. Use of a waste-derived catalyst according to claim 1, characterized by the possibility of combining the following steps: placing the catalyst particles or the honeycomb body in a reforming reactor, and enabling volatile components generated in the pyrolysis reaction process to pass through the reforming reactor at the temperature of 600-800 ℃, wherein tar in the volatile components is decomposed to obtain combustible gas; the combustion of said combustible gas is used to supply the thermal energy required for the anaerobic pyrolysis reaction and drying in step i) of preparing the catalyst.
9. Use of a waste-derived catalyst according to claim 1, characterized by the fact of being able to combine the following steps: after the catalyst from waste is utilized and failed at the temperature of 100-160 ℃ without reducing agent, pure N is introduced at the temperature of 600 DEG C2The gas is regenerated and can be reused.
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| CN109603841B (en) * | 2019-01-15 | 2019-10-25 | 武汉轻工大学 | A kind of decoking denitrating catalyst and its preparation method and application |
| CN110694609B (en) * | 2019-10-25 | 2022-07-19 | 中国林业科学研究院林产化学工业研究所 | Catalytic pyrolysis self-activation in-situ synthesis carbon-based La2O3Catalyst process and products thereof |
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| CN113926464B (en) * | 2021-11-10 | 2024-02-27 | 天津水泥工业设计研究院有限公司 | SCR catalyst using full-risk waste and solid waste as carriers and preparation method and application thereof |
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