CN115400756B - Non-noble metal catalyst for removing high-concentration laughing gas at low temperature and preparation method and application thereof - Google Patents
Non-noble metal catalyst for removing high-concentration laughing gas at low temperature and preparation method and application thereof Download PDFInfo
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- CN115400756B CN115400756B CN202211100533.8A CN202211100533A CN115400756B CN 115400756 B CN115400756 B CN 115400756B CN 202211100533 A CN202211100533 A CN 202211100533A CN 115400756 B CN115400756 B CN 115400756B
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- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 235000013842 nitrous oxide Nutrition 0.000 title claims abstract description 54
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005751 Copper oxide Substances 0.000 claims abstract description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002270 dispersing agent Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 150000001879 copper Chemical class 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 241000779819 Syncarpia glomulifera Species 0.000 claims description 3
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229960004488 linolenic acid Drugs 0.000 claims description 3
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001739 pinus spp. Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 229940036248 turpentine Drugs 0.000 claims description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- LKOVPWSSZFDYPG-WUKNDPDISA-N trans-octadec-2-enoic acid Chemical compound CCCCCCCCCCCCCCC\C=C\C(O)=O LKOVPWSSZFDYPG-WUKNDPDISA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 14
- 238000011161 development Methods 0.000 abstract description 7
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 238000012824 chemical production Methods 0.000 description 3
- 239000005431 greenhouse gas Substances 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000005481 linolenic acid group Chemical group 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing 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
- B01J23/70—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
- 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
-
- B01J35/40—
-
- B01J35/613—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/202—Hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/204—Carbon monoxide
Abstract
The invention discloses a non-noble metal catalyst for removing high-concentration laughing gas at low temperature, a preparation method and application thereof, belonging to the field of environmental protection and being capable of relieving the problems of greenhouse effect and the like. The copper-based catalyst is a main catalyst which is copper oxide and a cocatalyst which is iron oxide. The catalyst is prepared by adopting the processes of solution heat synthesis, planetary ball milling and the like, does not need auxiliary agents such as a carrier, a binder and the like, and has simple preparation process, low cost and good economic benefit. The non-noble metal copper-based catalyst provided by the invention has good performance in removing high-concentration laughing gas at low temperature, and the removal rate can reach more than 90% when the volume fraction of laughing gas is 10% at 300 ℃. The process relieves the problem of laughing gas pollution under the condition of low cost, has good economic benefit and social benefit, and meets the requirement of green low-carbon development.
Description
Technical Field
The invention relates to a non-noble metal catalyst for removing high-concentration laughing gas at low temperature, which is applied to occasions where laughing gas pollution is generated in the chemical production process. The technology belongs to the field of air pollution control, the field of clean production of nylon chemical industry and the field of industrial catalytic reaction engineering.
Background
Laughing gas (N) 2 O) is one of six greenhouse gases, the greenhouse effect being about 310 times that of carbon dioxide, and has been listed in the "united nations climate change framework convention", which, due to its extremely stable nature, can remain in the atmosphere for a long period of time up to about 150 years. The main hazard of laughing gas is to destroy the ozone layer, form ozone layer cavities, and finally cause greenhouse effect. Laughing gas is known to be the most damaging substance to the ozone layer at present, and its Global Warming Potential (GWP) is about CO 2 300 times of (2). The relevant literature indicates that N 2 O is growing at a rate of 0.2% per year, i.e. it is slowly eroding our ozone layer and causing damage. In the atmosphereN of (2) 2 O mostly comes from tail gas discharged from industrial production, and the largest discharge amount is generated in the industrial production process of adipic acid and nylon-66; other sources are automobile exhaust, biomass combustion, waste water, municipal solid waste and the like. N (N) 2 O is extremely stable in chemical nature, and how it is decomposed or treated to reduce N 2 The impact of O on atmospheric pollution is a research hotspot in the chemical field in recent years.
In recent years, a great deal of extreme weather appears in the world, the risk of methane overflow under ice is gradually increased due to the fact that the arctic temperature rise is caused in the world, once a great deal of greenhouse gas methane is released into the atmosphere, the greenhouse effect is increased, and catastrophic vicious circle is formed, so that the greenhouse effect is relieved, and the reduction of laughing gas emission is a key problem for safety of people and living of living organisms in the world.
The chemical industry is closely related to our life, is an indispensable important component in the economic development of China, and promotes the economic development of China. At present, the environmental pollution problem caused by chemical production is very serious, and along with the national advocated sustainable development strategy, the green chemical technology is gradually developed. Considering the factors such as cost and environmental pollution comprehensively, nitric acid is widely used as an oxidant in chemical production, and has the main defects of by-product of a large amount of nitrogen oxides, wherein nitric oxide and nitrogen dioxide are easily oxidized and recovered, and laughing gas has high thermodynamic stability and is difficult to treat. Adipic acid is a main intermediate for producing nylon-66 in nylon industry chains, and the adipic acid is generally produced by adopting a nitric acid oxidation process, which is relatively mature, and difficult to produce laughing gas in production.
In view of this, the present invention has been made. The invention provides a catalytic oxidation method for removing laughing gas generated in the nitric acid industry by adopting non-noble metals. The process has the advantages of low cost and good treatment effect, solves the problem of laughing gas emission, and relieves global warming effect.
Disclosure of Invention
Aiming at the problem that laughing gas is difficult to treat in the prior nitric acid oxidation process, the invention provides a non-noble metal copper-based catalyst for removing high-concentration laughing gas at a low temperature, and solves the problem that the laughing gas treatment process is harsh, high in energy consumption, high in cost and the like and is difficult to treat.
In order to solve the technical problems, the invention adopts the following technical scheme:
the non-noble metal catalyst for removing high-concentration laughing gas at low temperature is a copper-based catalyst, the copper-based catalyst uses copper oxide as a main catalyst, uses iron oxide as a cocatalyst, does not need auxiliary agents such as a carrier, a binder and the like, wherein the mass fraction of the copper oxide is 20-90 w.t%, the rest is the iron oxide, and the specific surface area of the non-noble metal catalyst is 10-50m 2 And/g, the particle size is 0.1-20 microns, and the particle size is mainly concentrated in small particles with the large size of about 10 microns and about 100 nanometers.
The preparation method of the non-noble metal catalyst for removing high-concentration laughing gas at low temperature comprises the following steps:
(1) Adding copper salt and ferric salt into a mixed solvent consisting of a high-viscosity solvent and a low-viscosity solvent, and stirring until the copper salt and the ferric salt are completely dissolved to form a double-solvent metal salt solution;
(2) Adding a water-soluble dispersing agent and an oil-soluble dispersing agent into the double-solvent metal salt solution obtained in the step (1), and stirring to obtain a mixed solution;
(3) Adding sodium hydroxide into the mixed solution obtained in the step (2), and vigorously stirring to obtain a mixed suspension;
(4) Transferring the mixed suspension obtained in the step (3) to a dynamic crystallization kettle for crystallization;
(5) Centrifugally separating the suspension crystallized in the step (4) to obtain a solid substance, washing with deionized water for three times and washing with ethanol for three times to obtain a washed solid;
(6) Putting the solid cleaned in the step (5) into a planetary ball milling tank for ball milling, and washing a sample obtained after ball milling by adopting ethanol;
(7) And (3) placing the ball-milled and washed sample in the step (6) in a blast drying oven for drying, and placing the dried sample in a muffle furnace for calcining to obtain the non-noble metal catalyst for removing high-concentration laughing gas at low temperature.
Further, the high-viscosity solvent in the step (1) refers to a solvent with a viscosity of more than 1.5 mPa.s at 20 ℃ and comprises n-propanol, n-butanol, isobutanol, glycerol and dimethyl sulfoxide, and the low-viscosity solvent comprises water, ethanol, methanol and n-hexane, and the volume ratio of the high-viscosity solvent to the low-viscosity solvent is (1-8): 1.
Further, the copper salt in the step (1) adopts one or more of inorganic copper salt and/or organic copper salt, and the iron salt adopts one or more of inorganic iron salt and/or organic iron salt; the mol ratio of the copper salt to the ferric salt is (0.7-2.5): 1.
Further, the water-soluble dispersing agent in the step (2) refers to a dispersing agent with better solubility in water, and comprises PVP, gelatin and polyethylene glycol; the oil-soluble dispersant refers to a dispersant with better oil solubility, such as turpentine (natural extract), oleylamine, octadecenoic acid and the like; the mass ratio of the oil-soluble dispersing agent to the water-soluble dispersing agent is (0.1-1): 1; in the mixed solution, the total concentration of the two dispersing agents is 0.01-0.1g/ml; the stirring speed is 100-150rpm, and the stirring time is 1-1.5 hours.
Further, the molar number of sodium hydroxide added in the step (2) is 1 to 1.5 times of the sum of the molar numbers of the ferric salt and the cupric salt in the raw material; the rotation speed of the vigorous stirring is 200-400rpm, and the vigorous stirring time is 2-6 hours.
Further, the crystallization temperature in the step (3) is 160-240 ℃ and the crystallization time is 12-24 hours.
Further, the ball milling in the planetary ball milling tank in the step (6) means that the sample is subjected to physical impact after hydrothermal treatment, including physical treatment processes such as ball milling, sand milling, grinding and the like; the rotating speed of ball milling in the planetary ball milling tank in the step (6) is 150rpm, the ball milling agent adopts linolenic acid, and the ball milling time is 1-2 hours.
Further, the drying temperature in the step (7) is 80 ℃, the drying time is 12 hours, the calcining temperature is 360 ℃, and the calcining time is 6 hours.
The invention relates to an application of a non-noble metal catalyst for removing high-concentration laughing gas at low temperature in removing high-concentration laughing gas at low temperature, which comprises the following steps: reducing substances including carbon monoxide, hydrogen and the like are added in the process of removing the high-concentration laughing gas; the low temperature is 250-350 ℃, and the volume concentration of the high concentration laughing gas is 1-50%, preferably 10%.
The invention adopts the reaction of the reducing gas and nitrous oxide (laughing gas) in the nitric acid oxidation section aiming at the generated nitrogen oxide waste gas to realize the goal of removing the laughing gas at low temperature, and the process solves the problem of treating the waste gas laughing gas under mild conditions with lower cost, thereby relieving the global warming effect.
The invention has the beneficial effects that: 1. the catalyst prepared by the invention has good catalytic performance, can promote the rapid reaction of reducing gas hydrogen or carbon monoxide and laughing gas, and solves the problem of waste gas treatment. 2. The catalyst used in the invention is a non-noble metal catalyst, copper and iron with low cost are used as catalyst active elements, the cost is low, the treatment condition is mild, the energy consumption is low, and the development concept of green chemical industry is met. Therefore, the invention has good application prospect, has the advantages of low cost, mild treatment condition and the like, and accords with the development trend of green chemical industry.
Drawings
FIG. 1 is a scanning electron microscope image of a non-noble metal copper-based catalyst according to example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. The specific embodiments described herein are to be considered in an illustrative sense only and are not intended to limit the invention.
Example 1
The preparation method of the non-noble metal catalyst in the embodiment is as follows:
(1) Firstly, weighing 4.0g of ferric trichloride hexahydrate and 2.4g of copper nitrate, dispersing the ferric trichloride hexahydrate and the copper nitrate into 50ml of glycerin and 10ml of deionized water solution, placing the suspension into an ultrasonic dispersing instrument for ultrasonic dispersion for 15 min for stirring until the suspension is uniformly mixed to form a double-solvent metal salt solution;
(2) Then adding 2.0g of water-soluble dispersant polyvinylpyrrolidone (K30), 0.5g of oil-soluble dispersant turpentine, and stirring for 1 hour at the rotating speed of 100rpm uniformly; then adding 2.8g of sodium carbonate into the mixture, and stirring vigorously for 3 hours at a mechanical stirring speed of 300rpm to obtain a suspension;
(3) Transferring the stirred suspension to a dynamic crystallization kettle, and maintaining the temperature at 180 ℃ for 12 hours;
(4) Centrifugally separating the crystallized suspension at 9000rpm to obtain a solid substance, washing with deionized water for three times and washing with ethanol for three times to obtain a washed solid;
(5) Placing the cleaned solid into a planetary ball milling tank for ball milling, wherein the rotating speed is 150rpm, the ball milling agent is linolenic acid, and the sample is washed with ethanol for three times after ball milling for 1 hour;
(6) And (3) drying the ball-milled and washed sample in a blast drying oven at 80 ℃ for 12 hours, and calcining in a muffle furnace for 6 hours at 360 ℃ to obtain the copper-based catalyst. The catalyst was named: CF-1.
Laughing gas removal reaction example
N was carried out in a fixed bed reactor 2 The reaction performance evaluation of O removal comprises the following specific steps:
catalyst evaluation was carried out in a fixed bed stainless steel tube reactor, a layer of quartz sand having 20 to 80 mesh particles was first packed in the reactor of the catalyst evaluation apparatus, and then 0.1g of catalyst CF-1 was charged into the reactor. After the air tightness is detected, the catalyst is pretreated to have catalytic activity. The nitrogen is used for activation, the gas flow is 40ml/min, the activation temperature is 300 ℃, the pressure is 0.1MPa, and the time is 5 hours, so that the catalyst can be fully activated. After activation, the activity of the catalyst was evaluated under the conditions of a reaction temperature of 300℃and a reaction pressure of 0.1MPa, a laughing gas flow rate of 20ml/min, a carbon monoxide flow rate of 20ml/min and an argon flow rate of 160 ml/min. After the reaction is in a stable state, experimental data are collected, after the stable reaction is carried out for 4 hours, sampling is carried out, and the sample enters a gas chromatograph through a three-way valve to carry out product analysis.
Reaction results: the conversion rate of laughing gas is 89.7%.
Example 2
As in example 1, 2.7g of ferric trichloride hexahydrate and 3.6g of copper nitrate were weighed and dispersed in 50ml of ethylene glycol to obtain catalyst CF-2, and 0.1g of catalyst CF-2 was charged into the reactor in the laughing gas removal reaction example. Otherwise, the same as in example 1 was conducted.
Example 3
As in example 1, 4.0g of ferric trichloride hexahydrate and 2.4g of copper nitrate were weighed, dispersed in 50ml of ethylene glycol and 10ml of deionized water solution, and 0g of water type dispersant polyvinylpyrrolidone was added to obtain catalyst CF-3, and 0.1g of catalyst CF-3 was charged into the reactor in the laughing gas removal reaction example. Otherwise, the same as in example 1 was conducted.
Example 4
As in example 1, 4.0g of ferric trichloride hexahydrate and 2.4g of copper nitrate were weighed, and a catalyst CF-4 was obtained without planetary ball milling treatment, and 0.1g of the catalyst CF-4 was charged into a reactor in the laughing gas removal reaction example. Otherwise, the same as in example 1 was conducted.
Example 5
As in example 1, the flow rate of reducing gas hydrogen gas was 20ml/min in the example of laughing gas removal reaction, and the other steps were as in example 1.
Example 6
The catalyst loading was 0g as in example 1, and the same as in example 1.
The evaluation results of the examples are shown in Table 1.
Table 1 results of catalyst evaluation
As can be seen from Table 1, the addition of catalyst CF-1 promotes the conversion of laughing gas in example 1 as compared to example 6. In the absence of a catalyst, laughing gas is hardly reduced.
Also, example 2 demonstrates that the catalyst activity is reduced when the catalyst is prepared using a single solvent, but also has a certain catalytic activity, compared with example 1, illustrating the effect of the di-dispersant on catalyst performance.
Example 3 the elimination of the aqueous dispersant compared to example 1 also resulted in a decrease in catalyst activity, a decrease in dispersant, and possibly agglomeration or non-uniformity of dispersion, thereby decreasing catalyst activity.
Example 4 the elimination of the ball milling process also resulted in a decrease in catalyst activity compared to example 1, and the ball milling process destroyed the dispersant on the catalyst surface, leaving more active sites exposed, facilitating the catalytic reaction.
Example 5 shows that the different reducing gases all exhibit good catalytic activity over the CF-1 catalyst and are universal compared to example 1.
The above examples show that the copper-based catalyst has the performance of catalyzing the reaction of reducing gas and laughing gas, and provides a new process and thought for treating laughing gas in the nitric acid oxidation industry chain. Solves the problem of treating waste gas laughing gas, reduces the emission of greenhouse gases at lower cost, and accords with the development trend of green chemical industry.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The preparation method of the non-noble metal catalyst for removing high-concentration laughing gas at low temperature is characterized by comprising the following steps:
(1) Adding copper salt and ferric salt into a mixed solvent consisting of a high-viscosity solvent and a low-viscosity solvent, and stirring until the copper salt and the ferric salt are completely dissolved to form a double-solvent metal salt solution;
(2) Adding a water-soluble dispersing agent and an oil-soluble dispersing agent into the double-solvent metal salt solution obtained in the step (1), and stirring to obtain a mixed solution;
(3) Adding sodium hydroxide into the mixed solution obtained in the step (2), and vigorously stirring to obtain a mixed suspension;
(4) Transferring the mixed suspension obtained in the step (3) to a dynamic crystallization kettle for crystallization;
(5) Centrifugally separating the suspension crystallized in the step (4) to obtain a solid substance, washing with deionized water for three times and washing with ethanol for three times to obtain a washed solid;
(6) Putting the solid cleaned in the step (5) into a planetary ball milling tank for ball milling, and washing a sample obtained after ball milling by adopting ethanol;
(7) Placing the ball-milled and washed sample obtained in the step (6) in a blast drying oven for drying, and then placing the dried sample in a muffle furnace for calcining to obtain the non-noble metal catalyst for removing high-concentration laughing gas at low temperature;
the non-noble metal catalyst is a copper-based catalyst, the copper-based catalyst takes copper oxide as a main catalyst and iron oxide as a cocatalyst, wherein the mass fraction of the copper oxide is 20-90 w.t%, and the balance is the iron oxide, and the specific surface area of the non-noble metal catalyst is 10-50m 2 And/g, the particle size is 0.1-20 microns.
2. The method for preparing the non-noble metal catalyst for removing the high-concentration laughing gas at the low temperature according to claim 1, which is characterized in that: the high-viscosity solvent in the step (1) refers to a solvent with the viscosity of more than 1.5 mPa.s at 20 ℃ and comprises n-propanol, n-butanol, isobutanol, glycerol and dimethyl sulfoxide, and the low-viscosity solvent comprises water, ethanol, methanol and n-hexane, and the volume ratio of the high-viscosity solvent to the low-viscosity solvent is (1-8): 1.
3. The method for preparing the non-noble metal catalyst for removing the high-concentration laughing gas at the low temperature according to claim 1, which is characterized in that: the copper salt in the step (1) adopts one or more of inorganic copper salt and/or organic copper salt, and the ferric salt adopts one or more of inorganic ferric salt and/or organic ferric salt; the mol ratio of the copper salt to the ferric salt is (0.7-2.5): 1.
4. The method for preparing the non-noble metal catalyst for removing the high-concentration laughing gas at the low temperature according to claim 1, which is characterized in that: the water-soluble dispersing agent in the step (2) comprises PVP, gelatin and polyethylene glycol; the oil-soluble dispersant comprises turpentine, oleylamine and octadecenoic acid; the mass ratio of the oil-soluble dispersing agent to the water-soluble dispersing agent is (0.1-1): 1; the total concentration of the two dispersants in the mixed solution is 0.01-0.1g/mL; the stirring speed is 100-150rpm, and the stirring time is 1-1.5 hours.
5. The method for preparing the non-noble metal catalyst for removing the high-concentration laughing gas at the low temperature according to claim 1, which is characterized in that: the mole number of sodium hydroxide added in the step (2) is 1-1.5 times of the sum of the mole numbers of ferric salt and cupric salt in the raw material; the rotation speed of the vigorous stirring is 200-400rpm, and the vigorous stirring time is 2-6 hours.
6. The method for preparing the non-noble metal catalyst for removing the high-concentration laughing gas at the low temperature according to claim 1, which is characterized in that: the crystallization temperature in the step (3) is 160-240 ℃ and the crystallization time is 12-24 hours.
7. The method for preparing the non-noble metal catalyst for removing the high-concentration laughing gas at the low temperature according to claim 1, which is characterized in that: the rotating speed of ball milling in the planetary ball milling tank in the step (6) is 150rpm, the ball milling agent adopts linolenic acid, and the ball milling time is 1-2 hours.
8. The method for preparing the non-noble metal catalyst for removing the high-concentration laughing gas at the low temperature according to claim 1, which is characterized in that: the drying temperature in the step (7) is 80 ℃, the drying time is 12 hours, the calcining temperature is 360 ℃, and the calcining time is 6 hours.
9. The use of a non-noble metal catalyst for removing high concentration laughing gas at low temperature according to any one of the preparation methods of claims 1 to 8, wherein: reducing substances are added in the process of removing the high-concentration laughing gas, and the reducing substances comprise carbon monoxide and hydrogen; the low temperature is 250-350 ℃, and the volume concentration of the high concentration laughing gas is 1-50%.
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