CN114733555A - Flame-retardant porous matrix supported noble metal catalyst, preparation method and application thereof - Google Patents
Flame-retardant porous matrix supported noble metal catalyst, preparation method and application thereof Download PDFInfo
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- CN114733555A CN114733555A CN202110024264.0A CN202110024264A CN114733555A CN 114733555 A CN114733555 A CN 114733555A CN 202110024264 A CN202110024264 A CN 202110024264A CN 114733555 A CN114733555 A CN 114733555A
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- Prior art keywords
- flame
- combination
- noble metal
- catalyst
- retardant
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- 239000011159 matrix material Substances 0.000 title claims abstract description 136
- 239000003054 catalyst Substances 0.000 title claims abstract description 131
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000003063 flame retardant Substances 0.000 title claims abstract description 125
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 22
- 229910001868 water Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000002351 wastewater Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims description 102
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 83
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 60
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 58
- 229910052697 platinum Inorganic materials 0.000 claims description 55
- 239000011148 porous material Substances 0.000 claims description 54
- 239000002253 acid Substances 0.000 claims description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 50
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- 239000002243 precursor Substances 0.000 claims description 42
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- 229910052763 palladium Inorganic materials 0.000 claims description 36
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- 239000011147 inorganic material Substances 0.000 claims description 28
- 239000002808 molecular sieve Substances 0.000 claims description 27
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 27
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- -1 group A: li Inorganic materials 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
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- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910052702 rhenium Inorganic materials 0.000 claims description 7
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
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- 229910052792 caesium Inorganic materials 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
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- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
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- QWDUNBOWGVRUCG-UHFFFAOYSA-N n-(4-chloro-2-nitrophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1[N+]([O-])=O QWDUNBOWGVRUCG-UHFFFAOYSA-N 0.000 description 1
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
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- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
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- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
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- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- UXMRNSHDSCDMLG-UHFFFAOYSA-J tetrachlororhenium Chemical compound Cl[Re](Cl)(Cl)Cl UXMRNSHDSCDMLG-UHFFFAOYSA-J 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- 229910052905 tridymite Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/123—X-type faujasite
-
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
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Abstract
The invention relates to a flame-retardant porous matrix supported noble metal catalyst, a preparation method and application thereof. The flame-retardant porous matrix supported noble metal catalyst has the advantages of simple preparation method, high mechanical strength, strong water and heat resistance, good catalytic conversion performance of volatile organic compounds in VOCs treatment, long service life and the like, and can be suitable for catalytic wet oxidation of wastewater.
Description
Technical Field
The invention relates to a flame-retardant porous matrix supported noble metal catalyst. More particularly, the invention relates to a flame-retardant porous matrix supported noble metal catalyst and a preparation method thereof. The invention also relates to application of the flame-retardant porous matrix supported noble metal catalyst in catalytic oxidation treatment of volatile organic compounds and high COD wastewater.
Background
With the increasing national requirements for environmental protection in recent years, recovery technologies such as adsorption, absorption, condensation, membrane separation, high-temperature incineration, and catalytic oxidation have been widely used for recovery/treatment of various waste gases containing Volatile Organic Compounds (VOCs). Wherein the adsorption method is suitable for 500-3000 h-1The treatment of removing low-concentration volatile organic pollutants in the waste gas at a low space velocity, particularly, a porous matrix adsorption and interception mode is adopted to adsorb high-boiling-point components (more than C5) on the surface or pore channels of the waste gas, the process hardly generates chemical reaction, and the matrix after adsorption saturation needs to be regenerated and desorbed to remove the volatile organic pollutantsThe re-adsorption performance is obtained, and the service cycle of the matrix is treated as dangerous solid waste after 1-2 years. The absorption method is based on the principle of similar phase and adopts a high-boiling point solvent (such as low-temperature diesel oil) to absorb high-boiling point components in VOCs to form a rich solution, and the rich solution is desorbed and then returns to a system for absorption again. The condensation method is a process of condensing organic substances into liquid by cooling and/or pressurizing according to different saturated vapor pressures of the organic substances at different temperatures, and removing and purifying the liquid from a gas phase. The membrane separation process can adopt organic polymeric membranes, inorganic membranes and biological membranes, but the membrane materials have the defects of low flux, poor selectivity, unsuitability for high space velocity treatment and the like. The high-temperature incineration has high requirement on the temperature, generally exceeds 800 ℃, although the high-temperature incineration can reach the standard for treatment, a large amount of auxiliary inflammable gas such as natural gas needs to be supplemented to keep the temperature of combustion, and the energy consumption is high.
Compared with the above methods, the catalytic oxidation method causes the organic waste gas to generate flameless combustion under the action of the catalyst, has the advantages of high selectivity, low reaction temperature and the like, the reaction temperature is generally lower than 500 ℃, and the product is nontoxic CO2And H2O, catalytic Oxidation non-methane Total hydrocarbons in volatile organics suitable for processing are generally above 500mg/m3. The most central of catalytic oxidation is a catalyst, which is divided into a noble metal catalyst and a transition metal oxide catalyst. Noble metal catalysts have the advantages of high activity, low light-off temperature, good stability, long service life and the like, but are expensive and not suitable for treating organic gases containing sulfur. The non-noble metal mainly takes transition metal oxide as a main component, and has better anti-poisoning performance and oxidation activity, but the catalyst has the defects of short service life, low activity, high ignition temperature and the like. ZL200510060542.9 discloses a preparation method of a rare earth composite porous alumina supported palladium catalyst, which takes honeycomb matrix ceramic as a carrier, adopts a sol dip coating method to coat hydrated alumina, a thermal adsorption method to support cerium-zirconium oxide and a supported metal palladium active component, and is used for 10000-30000 h-1Under the space velocity, the complete oxidation temperatures of the catalyst for toluene and ethyl acetate are 180-200 ℃ and 260-280 ℃, respectively, but the patent does not mention the influence of bromide on the activity and the service life of the catalyst. US4983366 disclosesA process for the catalytic conversion of exhaust gases containing hydrocarbons and carbon monoxide and a related purification unit are described, which process comprises passing the exhaust gases over a zeolite containing alumina, silica and/or oxides or barium, manganese, copper, chromium and nickel and over a catalyst containing platinum and/or palladium or rhodium, which catalyst is particularly suitable for treating the exhaust gases from vinyl chloride production units, but which catalyst does not mention the effect of a high strength substrate on the life of the noble metal catalyst. CN95197182.4 discloses a catalyst and a method for treating a gas containing halogenated organic compounds, non-halogenated organic compounds, carbon monoxide or a mixture thereof, the catalyst being characterized by containing at least one platinum group metal, zirconium oxide and at least one oxide of manganese, cerium or cobalt. CN200610047791.9 provides a method for purifying organic waste gas, especially for purifying organic waste gas containing acetaldehyde, ethylene glycol and PTA dust, such as polyester waste gas treatment method, wherein catalytic combustion adopts platinum, palladium or CuO, MnO containing2The honeycomb catalyst of (1). The clariant corporation in CN201810125199.9 discloses low cost ruthenium oxide based catalysts for VOC and halogenated VOC emission control, which catalysts include noble metals platinum based metals such as ruthenium and platinum, cerium zirconium solid solution, and tin oxide and silicon oxide, among other components. According to reports, the Envicat VOC catalyst developed by Craine has high efficiency of removing harmful Volatile Organic Compounds (VOCs) and carbon monoxide (CO), and simultaneously, the thermal energy consumption can be saved by 40 percent. CN201410455174.7 describes a catalyst comprising iron oxide, cobaltosic oxide, nickel oxide, copper oxide, vanadium oxide, chromium oxide, manganese dioxide or cerium oxide as non-noble metal oxide components, which are coated on a carrier to prepare a catalytic combustion catalyst for methane and other VOC gases.
In the above patent publications, alumina and titania are used as primary coating components in the catalyst coating process, and then active metal or active metal oxide is loaded, the stability of the coating not only affects the service life of the catalyst, but also the pressure drop of the fixed bed layer is increased and uncontrollable reaction factors are increased due to pulverization of the cracked and fallen coating. Therefore, much attention has been paid to the development of a catalyst which is excellent in thermal stability, high in strength, and excellent in the effect of supporting an active metal or an active metal oxide as a base (carrier).
Attapulgite clay (Attapulgite), also called Palygorskite (Palygorskite), is Attapulgite for short, is a natural hydrated clay material with a layered chain structure and rich in magnesium aluminum silicate, the basic structural unit is a sandwich structure of two layers of silicon-oxygen tetrahedron and one layer of magnesium (aluminum) oxygen octahedron, and the most ideal unit cell molecular formula is (Mg)5Si8O20(OH)2(OH2)4·4H2And O. The attapulgite clay has higher specific surface area, open meso-microporous composite pore canals and good thermal stability, and is mixed with molecular sieve and SiO2、Al2O3Similar to other materials, the materials all belong to inorganic mineral materials, have good adhesion performance and play a good role in enhancing and toughening organic and inorganic materials. The natural one-dimensional nano material attapulgite is used as an inner coating material of a honeycomb carrier and then precious metal is loaded for VOCs treatment, which is rarely reported in literatures.
Disclosure of Invention
In view of the technical problems in the prior art, the inventors of the present invention have assiduously studied on the basis of the prior art, and as a result, have found that a flame-retardant porous substrate can be prepared by using at least one selected from attapulgite and kaolin as an original substrate and further compounding an appropriate inorganic porous solid, and a noble metal component and an auxiliary component as catalyst active components are further supported on the substrate, so that the flame-retardant porous substrate supported noble metal catalyst of the present invention (hereinafter, sometimes also referred to as "flame-retardant porous substrate supported catalyst" or "catalyst of the present invention" or "catalyst") can be prepared. The flame-retardant porous matrix supported noble metal catalyst has good VOCs catalytic performance and high COD wastewater degradation performance, thereby completing the invention.
Specifically, the invention provides a noble metal catalyst loaded on a flame-retardant porous substrate, which is characterized by comprising the flame-retardant porous substrate, noble metal and an auxiliary agent component loaded on the flame-retardant porous substrate,
wherein the noble metal is at least one element selected from Pt, Pd, Ru, Rh, Au, Ir and Ag, preferably at least one combination selected from the combination of Pt and Pd, the combination of Pt and Ru, the combination of Pt and Au and the combination of Pt and Ir,
the additive component is at least one selected from the group A elements, the additive is preferably selected from at least one combination of Ce and Mo, Ce and Mn, Ce and Co, Ce and Fe, Ce and Ni, Ce and Bi, Ce and Cr, La and Mn, La and Fe, La and Co, La and Ni, La and Bi,
group A: li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce;
based on the total volume of the flame-retardant porous matrix supported noble metal catalyst, the content of noble metal (calculated by noble metal simple substance) is 100-1300 g/m3Preferably 150 to 1000 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200kg/m3Preferably 15 to 150 kg/m3，
The flame-retardant porous matrix comprises at least one original matrix selected from attapulgite and kaolin and at least one inorganic material selected from inorganic porous solids, wherein the content of the original matrix is 10-99.5 mass%, preferably 20-99 mass%, and the content of the inorganic material is 0.5-90 mass%, preferably 1-80 mass%, more preferably 5-80 mass%, even more preferably 8-70 mass%, and even more preferably the balance, based on the total mass of the porous matrix.
The invention also provides a preparation method of the flame-retardant porous matrix supported noble metal catalyst, which is characterized by comprising the following steps of:
(1) mixing and contacting at least one original matrix selected from attapulgite and kaolin, at least one inorganic material selected from inorganic porous solids, peptizing agent and water to prepare a plastic mixed contact body; wherein the content of the original matrix is 10 to 99.5 mass%, preferably 20 to 99 mass%, and the content of the inorganic material is 0.5 to 90 mass%, preferably 1 to 80 mass%, more preferably 5 to 80 mass%, further preferably 8 to 70 mass%, and further preferably the balance, with respect to the total amount of the original matrix and the inorganic material;
(2) optionally, molding the plastic mixed contact body to obtain a porous matrix blank;
(3) roasting the mixed contact body obtained in the step (1) or the porous matrix blank obtained in the step (2) to obtain a flame-retardant porous matrix;
(4) contacting a solution or suspension of a precursor of at least one precious metal component and a solution or suspension of a precursor of at least one auxiliary component with the flame-retardant porous matrix to obtain a contact product; and
(5) and roasting the contact product to obtain the flame-retardant porous matrix supported catalyst.
The invention also provides application of the flame-retardant porous matrix supported catalyst in catalytic oxidation of volatile organic compounds.
The invention also provides application of the flame-retardant porous matrix supported catalyst in catalytic oxidation of high-COD wastewater.
Technical effects
The preparation method of the flame-retardant porous matrix supported catalyst is simple, does not need vacuum pugging and microwave heat treatment, and is low in cost.
The flame-retardant porous matrix supported catalyst has good hydrothermal property, can be used for treating VOCs with high water vapor content and wastewater with high COD (chemical oxygen demand), and keeps excellent stability.
In the flame-retardant porous matrix supported catalyst, the supported metal and the porous matrix have strong interaction, so that coating loading on the porous matrix is not required, metal components are not easy to fall off, and the service life of the catalyst is long.
In addition, due to the porosity of the flame-retardant porous matrix supported catalyst, active components can be in full contact with VOCs, so that catalytic treatment of the VOCs is facilitated, in addition, the catalyst can be in full contact with high-COD substances in wastewater, and catalytic wet oxidation is facilitated, so that COD is reduced.
Detailed Description
Embodiments of the present invention will be described in more detail below with reference to specific embodiments, but those skilled in the art will understand that the following description of the embodiments is only for illustrating the present invention and should not be construed as limiting the scope of the present invention. On the contrary, the invention is intended to cover all alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims.
Unless otherwise specified, the embodiments of the present invention may be combined in any manner, and the resulting changes, modifications, and alterations of the technical solutions are also included in the scope of the present invention, and do not exceed the scope of the present invention.
The invention provides a noble metal catalyst loaded on a flame-retardant porous matrix, which is characterized by comprising the flame-retardant porous matrix, noble metal and an auxiliary agent component loaded on the flame-retardant porous matrix,
wherein the noble metal is at least one element selected from Pt, Pd, Ru, Rh, Au, Ir and Ag, preferably at least one combination selected from the combination of Pt and Pd, the combination of Pt and Ru, the combination of Pt and Au and the combination of Pt and Ir,
the additive component is at least one selected from the group A elements, the additive is preferably selected from at least one combination of Ce and Mo, Ce and Mn, Ce and Co, Ce and Fe, Ce and Ni, Ce and Bi, Ce and Cr, La and Mn, La and Fe, La and Co, La and Ni, La and Bi,
group A: li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce;
based on the total volume of the flame-retardant porous matrix supported noble metal catalyst, the content of noble metal (calculated by the simple substance of the noble metal) is 100-1300 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200kg/m3，
The flame-retardant porous matrix comprises at least one original matrix selected from attapulgite and kaolin and at least one inorganic material selected from inorganic porous solids, wherein the content of the original matrix is 10-99.5 mass%, preferably 20-99 mass%, and the content of the inorganic material is 0.5-90 mass%, preferably 1-80 mass%, more preferably 5-80 mass%, even more preferably 8-70 mass%, and even more preferably the balance, based on the total mass of the porous matrix.
In one embodiment of the invention, the porous matrix consists essentially of the original matrix and the inorganic material. In one embodiment of the present invention, the porous matrix consists only of the original matrix and the inorganic material.
In one embodiment of the present invention, the content of the original matrix is 10 to 99.5 mass%, preferably 20 to 99 mass%, based on the total mass of the porous matrix.
In one embodiment of the present invention, the inorganic material is contained in an amount of 0.5 to 90 mass%, preferably 1 to 80 mass%, more preferably 5 to 80 mass%, further preferably 8 to 70 mass%, and further preferably the balance, based on the total mass of the porous matrix.
In the present invention, the attapulgite known in the art may be used as the attapulgite, and commercially available attapulgite may be used. The kaolin may be kaolin known in the art, which may be commercially available.
In the present invention, the inorganic porous solid includes refractory oxides of metals of group IIA, IIIA, IVA or IVB of the periodic table of elements (for example, silica (also referred to as silica or silica gel), alumina, magnesia, titania, zirconia, thoria, etc.), or any refractory composite oxides of these metals (for example, silica-alumina, magnesia-alumina, titania-silica, titania-magnesia, titania-alumina, etc.), and clays, molecular sieves, mica, montmorillonite, bentonite, diatomaceous earth, etc.
In one embodiment of the present invention, the inorganic porous solid is preferably at least one selected from the group consisting of silica, alumina, magnesia, silica alumina, magnesia alumina, titania silica, titania, a molecular sieve, and montmorillonite.
In the present invention, the molecular sieve may use a molecular sieve known in the art, for example, the molecular sieve may be selected from one or a combination of two or more of a type a molecular sieve, a type X molecular sieve, a type Y molecular sieve, a ZSM series, SAPO, AIPO, mordenite molecular sieve, SBA, MCM.
In the present invention, various inorganic materials known in the art can be used for silica, alumina, magnesia, silica-alumina, magnesia-alumina, titania-silica, titania, a molecular sieve and montmorillonite, and they can be produced by a known method or any commercially available product.
In one embodiment of the invention, the BET specific surface area of the flame-retardant porous matrix supported catalyst is 100-800 m2·g-1Preferably 110 to 800m2·g-1The most probable pore diameter is 2 to 16nm, preferably 4 to 12nm, and the pore volume is 0.15 to 1.0 ml/g-1Preferably 0.2 to 1.0 ml/g-1。
In one embodiment of the present invention, the flame retardant porous matrix-supported catalyst may be molded into a macroscopic molded body having an appearance of a sphere, a cube, a cuboid, a cylinder, a raschig ring, or the like.
In one embodiment of the present invention, when molded into a flame-retardant porous substrate-supported catalyst, the flame-retardant porous substrate-supported catalyst may have macroscopic channels, which may have one or more channel structures of a circular, square, triangular, hexagonal, or rhombic shape. The arrangement of the macroscopic pore channels on the flame-retardant porous matrix supported catalyst can be ordered or disordered, and uniform and ordered honeycomb pore channels are preferred. In general, to reduce adsorption resistance, macroscopic pores on the flame-retardant porous substrate-supported catalyst are open.
In one embodiment of the invention, on the macroscopic flame retardant porous substrate supported catalyst, the cross-sectional area of each macroscopic channel is 1mm2~80mm2Preferably 1mm2~35mm2. The thickness of the hole wall is 1-4 mm, preferably 1-2.5 mm.
In one embodiment of the invention, the flame-retardant porous matrix-supported catalyst has a positive pressure strength of 2-8MPa, preferably 3-6 MPa, and a lateral pressure strength of 0.1-2 MPa, preferably 0.25-1.5 MPa, measured according to the GB/T5072-2008 standard method.
The porous matrix may optionally further contain other auxiliary agents without impairing the effects of the present invention, and examples of the auxiliary agents include various metal oxides other than the above-mentioned inorganic materials, various inert organic porous solids, and the like. The amount of the adjuvant used is 5 to 30% of the total mass of the porous matrix.
In one embodiment of the invention, the catalyst consists essentially of a flame retarded porous substrate, at least one precious metal supported on the porous substrate, and an adjunct component.
In one embodiment of the invention, the catalyst consists only of the flame-retardant porous substrate, the at least one noble metal supported on the porous substrate, and the auxiliary component. In one embodiment of the invention, the catalyst does not contain carbonaceous materials (including but not limited to activated carbon, carbon fibers, etc.).
In one embodiment of the present invention, the noble metal is at least one element selected from Pt, Pd, Ru, Rh, Au, Ir, and Ag.
In one embodiment of the present invention, the noble metal is at least one selected from the group consisting of a combination of Pt and Pd, a combination of Pt and Ru, a combination of Pt and Au, and a combination of Pt and Ir, and the mass ratio of the two elements (the former to the latter) (in terms of the simple substance of the element) in each combination is preferably 0.2 to 5, and more preferably 0.4 to 4.
In one embodiment of the invention, the adjuvant component is at least one selected from the group consisting of group a elements, group a: li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce.
In one embodiment of the present invention, the auxiliary is preferably at least one selected from the group consisting of a combination of Ce and Mo, a combination of Ce and Mn, a combination of Ce and Co, a combination of Ce and Fe, a combination of Ce and Ni, a combination of Ce and Bi, a combination of Ce and Cr, a combination of La and Mn, a combination of La and Fe, a combination of La and Co, a combination of La and Ni, and a combination of La and Bi, and the mass ratio of the two elements (the former to the latter) (in terms of the element) in each combination is preferably 0.1 to 10, preferably 0.5 to 5.
In one embodiment of the invention, the content of the noble metal (calculated by the simple substance of the noble metal) is 100-1300 g/m based on the total volume of the noble metal catalyst supported by the flame-retardant porous matrix3Preferably 150 to 1000 g/m3。
In one embodiment of the invention, the content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200kg/m based on the total volume of the noble metal catalyst supported on the flame-retardant porous substrate3Preferably 15 to 150 kg/m3。
In one embodiment of the invention, in the noble metal catalyst supported on the flame-retardant porous substrate, the mass ratio of the noble metal Pt to other noble metals is 0.7: 1-8: 1.
The invention also provides a preparation method of the flame-retardant porous matrix supported noble metal catalyst, which is characterized by comprising the following steps of:
(1) mixing and contacting at least one original matrix selected from attapulgite and kaolin, at least one inorganic material selected from inorganic porous solids, peptizing agent and water to prepare a plastic mixed contact body; wherein the content of the original matrix is 10 to 99.5 mass%, preferably 20 to 99 mass%, and the content of the inorganic material is 0.5 to 90 mass%, preferably 1 to 80 mass%, more preferably 5 to 80 mass%, further preferably 8 to 70 mass%, and further preferably the balance, with respect to the total amount of the original matrix and the inorganic material;
(2) optionally, molding the plastic mixed contact body to obtain a porous matrix blank;
(3) roasting the mixed contact body obtained in the step (1) or the porous matrix blank obtained in the step (2) to obtain a flame-retardant porous matrix;
(4) contacting a solution or suspension of a precursor of at least one precious metal component and a solution or suspension of a precursor of at least one auxiliary component with the flame-retardant porous matrix to obtain a contact product; and
(5) roasting the contact product to obtain the flame-retardant porous matrix supported catalyst
In one embodiment of the present invention, in the step (1) of the above preparation method, the at least one original matrix selected from the group consisting of attapulgite and kaolin is not subjected to any pretreatment.
In the preparation method of the present invention, the attapulgite known in the art may be used, and may be a commercially available attapulgite. The kaolin may be kaolin known in the art, which may be commercially available.
In the preparation method of the present invention, in the step (1), the inorganic porous solid may be a refractory oxide of a metal of group IIA, IIIA, IVA or IVB of the periodic table of elements (for example, silica (also referred to as silica gel or silica gel), alumina, magnesia, titania, zirconia, thoria, or the like), or any refractory composite oxide of these metals (for example, silica alumina, magnesia alumina, titania silica, titania magnesia, titania alumina, etc.), clay, molecular sieve, mica, montmorillonite, bentonite, diatomaceous earth, or the like.
In one embodiment of the present invention, the inorganic porous solid is preferably at least one selected from the group consisting of silica, alumina, magnesia, silica alumina, magnesia alumina, titania silica, titania, a molecular sieve, and montmorillonite.
The molecular sieve may use a molecular sieve known in the art, for example, the molecular sieve may be selected from one or a combination of two or more of a type a molecular sieve, a type X molecular sieve, a type Y molecular sieve, a ZSM series, a SAPO, an AIPO, a mordenite molecular sieve, an SBA, and an MCM. Silica, alumina, magnesia, silica alumina, magnesia-alumina, titania-silica, molecular sieves and montmorillonite can be made of various materials known in the art by known methods, or any commercially available product.
In the preparation method of the present invention, in the step (1), the peptizing agent may be an organic or inorganic substance as long as it can disperse the original matrix and the inorganic material, and examples thereof include inorganic acids, inorganic bases, polycarboxylic acids, monohydric alcohols, polyhydric alcohols, polyamines, cellulose derivatives, and carboxylates. These peptizers may be used alone or in combination of two or more. The amount of the peptizing agent is not particularly limited, and may be adjusted according to the total amount of the base substrate and the inorganic material, and is preferably 1 to 20 parts by mass, preferably 1.2 to 10 parts by mass, and more preferably 1.5 to 5 parts by mass, based on 100 parts by mass of the total amount of the base substrate and the inorganic material.
As the inorganic acid, various types of inorganic acids known in the art can be used, and for example, one or a combination of two or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and perchloric acid can be cited.
The inorganic base may be an alkali metal hydroxide or an alkaline earth metal hydroxide, and examples thereof include one or a combination of two or more of sodium hydroxide, calcium hydroxide, potassium hydroxide, magnesium hydroxide, and lithium hydroxide.
As the polycarboxylic acid, various polycarboxylic acids known in the art can be used, and examples thereof include C having 2 to 10 (preferably 3 to 6) carboxyl groups2-20Examples of the alkane include oxalic acid, succinic acid, and adipic acid. The polycarboxylic acid may include C optionally having one or more hydroxyl groups (for example, 1 to 6) and 1 to 10 (preferably 3 to 6) carboxyl groups2-20Examples of the alkane include malic acid, tartaric acid, citric acid, and stearic acid. Alternatively, the polycarboxylic acid may be one represented by the formula C2-20Examples of the polycarboxyalkyl (poly) amine obtained by inserting one or more N atoms into an alkane chain include nitrilotriacetic acid and ethylenediaminetetraacetic acid.
As the monohydric alcohol, various monohydric alcohols known in the art can be used, and examples thereof include C having 1 hydroxyl group1-20Examples of the alkane include methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol.
As the polyol, various polyols known in the art can be used, and examples thereof include C having 2 to 10 (preferably 3 to 6) hydroxyl groups2-20Examples of the alkane include ethylene glycol, diethylene glycol, propylene glycol and glycerinPentaerythritol, or polymers of the polyhydric alcohol, such as polyethylene glycol, polyvinyl alcohol, and the like, or may be in the above-mentioned C2-20Examples of the polyhydroxyalkyl (poly) amine obtained by inserting one or more N atoms into an alkane chain include monoethanolamine and triethanolamine.
As the polyamine, various polyamines known in the art can be used, and examples thereof include ethylenediamine, diethylenetriamine, triethylenetetramine, and hexamethylenediamine.
As the cellulose derivative, those known in the art can be used, and examples thereof include methyl cellulose, hydroxymethyl propyl cellulose, carboxymethyl cellulose and the like.
As the carboxylate, those known in the art can be used, and examples thereof include magnesium stearate, sodium stearate, and the like.
In the step (1), the amount of water to be added is not particularly limited as long as the original matrix and the inorganic material can be dispersed. The amount of water is preferably 20 to 120 parts by mass with respect to 100 parts by mass of the total amount of the starting substrate and the inorganic material. In step (1), a contact body may be prepared by stirring using a kneader.
And (2) molding the plastic mixed contact body to obtain a porous matrix blank. The equipment and conditions for the molding process are not particularly limited, and those known in the art may be used.
In the step (2), an extruder can be used for molding during molding, the pressure in the charging barrel reaches 0.5-8 MPa, preferably 1-6 MPa, and the extrusion temperature of the charging barrel is 20-80 ℃.
The blank can be molded into various shapes according to requirements, such as a sphere, a cube, a cuboid, a cylinder and a raschig ring. The embryo body can have circular, square, triangular, hexagonal or rhombic macroscopic pores. The macro-channels are preferably uniformly ordered through-going honeycomb channels.
And (3) roasting the porous matrix blank to obtain the flame-retardant porous matrix.
The calcination temperature in the step (3) is not particularly limited, and the temperature may be 200 to 580 ℃, preferably 200 to 550 ℃, and more preferably 300 to 550 ℃. The baking time may be 1 to 20 hours, preferably 2 to 20 hours, and more preferably 4 to 16 hours. The calcination may be carried out in air or in an inert gas atmosphere. Examples of the inert gas include nitrogen gas and a rare gas, and nitrogen gas is preferable.
In the production method of the present invention, the step (2) is an optional step, and in the case where the step (2) is not provided, the plastic mixed contact body in the step (1) is subjected to a firing treatment in the step (3). The firing conditions are the same as described above.
Immediately before the step (3) of the present invention, a heat treatment may be optionally performed, wherein the plastic mixed contact body in the step (1) or the porous base body in the step (2) is subjected to a heat treatment step such as drying, airing, air drying, or the like to remove moisture in the contact body or the porous base body, and the heat treatment is performed at 20 to 150 ℃, preferably 30 to 120 ℃, and more preferably 50 to 100 ℃.
According to the present invention, in the contacting step of said step (1), the order of contacting the respective raw material components (i.e., at least one original matrix selected from attapulgite and kaolin, at least one inorganic material selected from inorganic porous solids, and peptizing agent, water) is not particularly limited.
According to the present invention, in the step (1), the contacting step is not particularly limited in the manner of carrying out, as long as sufficient mixing and contacting of the respective raw material components can be achieved to form a uniform contact product. For example, the raw material components may be mixed (with additional stirring, if necessary) to homogeneity in any manner known in the art. In step (1), the contacting step may be carried out at any temperature of 0 ℃ to 150 ℃, for example, at room temperature.
In the step (4), the noble metal is at least one selected from Pt, Pd, Ru, Rh, Au, Ir, and Ag. The noble metal is preferably at least one combination selected from the group consisting of a combination of Pt and Pd, a combination of Pt and Ru, a combination of Pt and Au, and a combination of Pt and Ir, and the mass ratio of the two elements (the former to the latter) (in terms of the element) in each combination is preferably 0.2 to 5, more preferably 0.4 to 4.
In step (4), the auxiliary component comprises at least one element selected from group a: li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce. Preferably, the auxiliary agent is at least one combination selected from the group consisting of a combination of Ce and Mo, a combination of Ce and Mn, a combination of Ce and Fe, a combination of Ce and Co, a combination of Ce and Ni, a combination of Ce and Bi, a combination of Ce and Cr, a combination of La and Mn, a combination of La and Fe, a combination of La and Co, a combination of La and Ni, and a combination of La and Bi, and preferably, the mass ratio of the two elements (the former to the latter) (in terms of the elements) in each combination is 0.1 to 10, preferably 0.5 to 5.
In the present invention, the precursor of the noble metal component is a precursor of a noble metal commonly used in the art, for example, the precursor of the noble metal may be preferably a soluble salt and/or an acid of the noble metal, and further preferably a chloride, a nitrate, an acetate, a sulfate, an ammonia salt, and the like, but is not limited thereto. For example, the palladium metal precursor may be selected from palladium chloride, palladium nitrate, palladium acetate, palladium dichlorodiammine, etc., and the platinum metal precursor may be selected from chloroplatinic acid, platinum chloride, dinitrosopropylamine, platinum dichlorotetrammine, etc.
In the present invention, the precursor of the auxiliary component is a precursor of an auxiliary metal commonly used in the art, for example, the precursor of the auxiliary metal may be preferably a soluble salt of the auxiliary component, and further preferably a chloride salt, a nitrate, an acetate, a sulfate, an ammonia salt, or a phosphate. For example, cerium nitrate, cerium chloride, cerium ammonium nitrate, and the like may be selected as the cerium precursor.
In the present invention, the solvent used for preparing the solution or suspension of the precursor of the noble metal component or the solution or suspension of the precursor of the auxiliary component is not particularly limited, and various solvents known in the art may be used as long as the precursor of the noble metal component or the precursor of the auxiliary component can be dissolved or suspended and the effect of the present invention is not impaired. It can be various organic solvents or water, preferably deionized water. To the solvent, various kinds of inorganic acids (e.g., hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.), organic acids (e.g., formic acid, acetic acid, propionic acid, oxalic acid, etc.), and the like can be optionally added. The inorganic acid and the organic acid can function as a complexing agent, a stabilizer, and a pH adjuster as described below.
In the present invention, when the precursor of the noble metal component and the precursor of the auxiliary component are prepared as a solution or a suspension, the concentration of the solution or the suspension is not particularly limited, and may be usually 10 to 300 g/L.
In the present invention, various additives, for example, a complexing agent, a stabilizer, and a pH adjuster, may be further added as necessary when preparing a solution or suspension of a precursor of the noble metal component and/or when preparing a solution or suspension of a precursor of the auxiliary component.
Examples of the complexing agent include polycarboxylic acids, monohydric alcohols, polyhydric alcohols, and polyamines. These complexing agents may be used alone or in combination of two or more, as required. Examples of the polycarboxylic acid include C2-20 alkanes having 2 to 10 (preferably 3 to 6) carboxyl groups, and examples thereof include oxalic acid, succinic acid, and adipic acid. The polycarboxylic acid may be a C2-20 alkane having one or more hydroxyl groups (for example, 1 to 6) and 2 to 10 (preferably 3 to 6) carboxyl groups, and examples thereof include malic acid, tartaric acid, and citric acid. Alternatively, the polycarboxylic acid may be a polycarboxyalkyl (poly) amine obtained by inserting one or more N atoms into the C2-20 alkane chain, and examples thereof include nitrilotriacetic acid and ethylenediaminetetraacetic acid. Examples of the monohydric alcohol include C1-20 alkanes having 1 hydroxyl group, and examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol. Examples of the polyhydric alcohol include C2-20 alkanes having 2 to 10 (preferably 3 to 6) hydroxyl groups, such as ethylene glycol and glycerol, polymers of the polyhydric alcohol, such as polyethylene glycol, and polyhydroxyalkyl (poly) amines obtained by inserting one or more N atoms into the C2-20 alkane chain, such as monoethanolamine and triethanolamine. Examples of the polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine, and the like.
As the stabilizer, various stabilizers known in the art may be used, and for example, oxides of metals selected from barium, calcium, magnesium, strontium, and mixtures thereof may be used. The stabilizer preferably comprises one or more barium and/or strontium oxides.
As the pH adjuster, various pH adjusters known in the art can be used, and examples thereof include various water-soluble acids and water-soluble bases, such as hydroxy monocarboxylic acid, polyhydroxy monocarboxylic acid, hydroxy polycarboxylic acid, polyhydroxy polycarboxylic acid, and monocarboxylic acid; and alkaline substances such as ethylenediamine and ammonia water.
When the complexing agent having acidity or basicity is used, it can also function as a pH adjuster.
In the step (4) of bringing the solution or suspension of the precursor of the at least one noble metal component and the solution or suspension of the precursor of the at least one auxiliary component into contact with the flame-retardant porous substrate, the order of contacting the solution or suspension of the precursor of the noble metal component, the solution or suspension of the precursor of the auxiliary component, and the porous substrate is not limited at all. The solution or suspension of the precursor of the noble metal component may be contacted with the porous substrate first, and then the solution or suspension of the precursor of the auxiliary component may be contacted with the porous substrate, or the order may be changed. Or after respectively preparing a solution or suspension of a precursor of the noble metal component and a solution or suspension of a precursor of the auxiliary component, mixing the two solutions or suspensions, and simultaneously contacting the two solutions or suspensions with the flame-retardant porous matrix. In addition, between the two contacting steps, a heat treatment step such as drying and baking may be optionally performed, for example, at 50 to 180 ℃, preferably at 60 to 150 ℃, and more preferably at 70 to 120 ℃, followed by drying, air-drying, and air-drying.
In addition, in the invention, a precursor of the noble metal component and a precursor of the auxiliary agent component can be prepared into a solution or suspension together, and then the solution or suspension is contacted with the flame-retardant porous matrix. That is, in this case, "a solution or suspension of a precursor of the noble metal component" and "a solution or suspension of a precursor of the auxiliary component" mean the same solution or suspension.
In the step (4) of the present invention, the contact with the flame retardant porous substrate may be performed by spraying or showering the solution or suspension to the flame retardant porous substrate, or by immersing the flame retardant porous substrate in the solution or suspension. Preferably by impregnation. The contacting may be carried out at any temperature, for example at room temperature. The contact time is not particularly limited, so long as the content of the noble metal (in terms of the simple noble metal) in the finally prepared catalyst is 100 to 1300g/m based on the total volume of the catalyst3Preferably 150 to 1000 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200kg/m3Preferably 15 to 150 kg/m3And (4) finishing.
In the step (4), when the solution or suspension of the precursor of the precious metal component, the solution or suspension of the precursor of the auxiliary component and the flame-retardant porous matrix are contacted, the concentration of the solution or suspension of the precursor of the precious metal component, the concentration of the solution or suspension of the precursor of the auxiliary component and the contact time of the porous matrix and the solution or suspension of the porous matrix and the flame-retardant porous matrix can be adjusted, so that the content of precious metal (calculated by a precious metal simple substance) in the finally prepared catalyst is 100-1300 g/m based on the total volume of the catalyst3Preferably 150 to 1000 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200kg/m3Preferably 15 to 150 kg/m3And (4) finishing.
In one embodiment of the present invention, after the contacting step in each step, the resulting contact product may be directly used in the next step.
In one embodiment of the present invention, after the contacting step in each step, the obtained contact product may be further subjected to drying or the like, especially when the contact product is in slurry, by any means known in the art, for example, drying, airing, and air drying at 50 to 180 ℃, preferably 60 to 150 ℃, and more preferably 70 to 120 ℃ to remove any dispersion medium (such as water) that may be introduced during the preparation thereof. According to the invention, the dried contact product is also referred to as contact product.
In the invention, in the step (5), the contact product obtained in the step (4) is roasted to obtain the flame-retardant porous matrix supported noble metal catalyst.
In the step (5), the roasting temperature is 200-550 ℃, preferably 200-500 ℃, and further preferably 250-500 ℃. The calcination may be performed in an air atmosphere or an inert gas atmosphere. The heat treatment time is not particularly limited, and may be 2 to 20 hours, preferably 4 to 16 hours.
The flame-retardant porous matrix supported catalyst or the flame-retardant porous matrix supported catalyst prepared by the preparation method can be used for catalytic oxidation treatment of volatile organic compounds.
In one embodiment of the present invention, the conditions for catalytic oxidation treatment of volatile organic compounds are: the gas containing volatile organic compounds is enabled to have a gas volume space velocity of 4000-25000 h-1And contacting the porous matrix supported catalyst at the temperature of 150-450 ℃ to remove volatile organic gas by catalytic oxidation.
The flame-retardant porous matrix supported catalyst or the flame-retardant porous matrix supported catalyst prepared by the preparation method can be used for catalytic oxidation of wastewater, particularly wastewater containing high COD.
In one embodiment of the present invention, the conditions for the catalytic oxidation treatment of wastewater are: the space velocity of the liquid volume of the wastewater is 0.2 to 3h-1The pressure is 2-8MPa, the reaction temperature is 200-280 ℃, and the porous matrix is contacted with the catalyst to implement catalytic oxidation.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples. In the present invention, the content of each metal element is calculated as a simple substance unless otherwise specified.
In the present invention, the surface area is measured by a BET specific surface area measurement method.
The pore volume was determined by the BJH (Barrett-Joyner-Halenda) method.
The mode pore size was determined by BJH.
The cross-sectional area of individual honeycomb macrocells (also referred to simply as honeycomb cells) is calculated from the specific shape.
Specifically, when the cellular macroscopic pore canal is circular, square, triangular, hexagonal or rhombic, the sectional area can be calculated according to a conventional area calculation method; when the cellular macroscopic pore canal has an irregular shape, the longest diameter (or the longest diagonal length) and the shortest diameter (or the shortest diagonal length) of the shape are measured, and the cross section area = [ (the longest diameter (or the longest diagonal length) + the shortest diameter (or the shortest diagonal length))/4]2π. The sectional area of 10 honeycomb holes was calculated, and the average value thereof was taken as the sectional area of a single honeycomb hole.
The positive pressure strength and the lateral pressure strength are measured by a GB/T5072-2008 national standard method.
Example 1
Mixing attapulgite, a 13X molecular sieve, 65% nitric acid, methylcellulose and magnesium stearate in a mass ratio of 10: 3: 0.02:0.2: stirring the mixture evenly in a kneader according to the proportion of 0.001, adding a proper amount of water, kneading the mixture into a plastic mixed contact body, putting the contact body into an extruder, extruding and molding the mixture under the conditions that the temperature is 30 ℃ and the pressure is 5MPa to prepare a square honeycomb hole green body, wherein the side length and the height of four bottom edges of the square honeycomb hole green body are respectively 80cm and 100cm, and roasting the honeycomb green body in the air at the temperature of 500 ℃ for 12 hours to obtain the flame-retardant honeycomb matrix A. The Pt content in each cubic flame-retardant honeycomb substrate is 380g/m3The Ru content is 140g/m3Preparing a chloroplatinic acid solution and an oxalic acid aqueous solution of ruthenium chloride according to the proportion, wherein the mass ratio of oxalic acid to chloroplatinic acid is 3:1, and the Ce content in each cubic flame-retardant honeycomb matrix is 30kg/m3Sn content of 18kg/m3Preparing aqueous solution of cerium nitrate and stannous chloride according to the proportion, firstly soaking Pt and Ru solution in a flame-retardant honeycomb substrate A, and performing heat treatment at the temperature of 150 DEG CDrying for 4 hours, further soaking the Ce and Sn solution, drying again for 2 hours at 150 ℃, and roasting for 5 hours at 500 ℃ to obtain the flame-retardant porous matrix supported noble metal catalyst A1 with the surface area of 150m2g-1The most probable pore diameter is 5.5nm, and the pore volume is 0.41mlg-1The cross section of the honeycomb holes is 9.3mm2。
Example 2
Mixing attapulgite, kaolin, a Y molecular sieve, 65% nitric acid, methylcellulose and magnesium stearate in a mass ratio of 8: 2: 2:0.02:0.2:0.03, stirring uniformly in a kneading machine, adding a proper amount of water, kneading into a plastic mixed contact body, putting the contact body into an extruder, extruding and molding under the conditions that the temperature is 25 ℃ and the pressure is 5MPa to prepare a billet of square honeycomb holes, wherein the side length and the height of four bottom edges of the billet of the square honeycomb holes are 80cm and 100cm respectively, and the honeycomb billet is subjected to N-shaped extrusion molding2Roasting for 2 hours at 500 ℃ under the condition to obtain the flame-retardant honeycomb matrix B. The Pt content per cubic honeycomb substrate is 480g/m3Pd content of 120g/m3Preparing a chloroplatinic acid solution and an oxalic acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of oxalic acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic honeycomb matrix is 40kg/m3Mn content of 18kg/m3Preparing aqueous solution of cerium nitrate and manganese nitrate, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 150 ℃, then further soaking Ce and Mn solution, drying for 2 hours at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 500 ℃ to obtain the flame-retardant porous substrate supported noble metal catalyst B1 with the surface area of 143m2g-1The most probable pore diameter is 5.5nm, and the pore volume is 0.36mlg-1The cross section of the honeycomb holes is 9.1mm2。
Example 3
Mixing attapulgite, kaolin, an SBA-15 molecular sieve, 65 mass percent nitric acid, methylcellulose and magnesium stearate in a mass ratio of 7:3: 4: 0.02:0.2: stirring in kneader at a ratio of 0.03, adding appropriate amount of water, kneading to obtain plastic mixed contact body, and feeding the contact body into extruder at temperature ofExtruding and molding under the condition of 30 ℃ and 5MPa pressure to prepare a blank of square honeycomb holes, wherein the length and height of four bottom edges of the blank of the square honeycomb holes are respectively 80cm and 100cm, and the honeycomb blank is subjected to N2And roasting for 2 hours at 500 ℃ under the condition to obtain the flame-retardant honeycomb matrix C. The Pt content of each cubic honeycomb substrate is 500g/m3The Au content is 150g/m3Preparing a chloroplatinic acid solution and an oxalic acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of oxalic acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic honeycomb matrix is 40kg/m3The content of Co is 18kg/m3Preparing aqueous solution of cerous nitrate and cobalt nitrate according to the proportion, firstly soaking Pt and Au solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking Ce and Co solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 500 ℃ to obtain the flame-retardant porous substrate supported noble metal catalyst C1 with the surface area of 347m2g-1The most probable pore diameter is 6.8nm, and the pore volume is 0.54mlg-1The cross section of the honeycomb holes is 8.1mm2。
Example 4
Uniformly stirring attapulgite, kaolin, a 5A molecular sieve, 65 mass percent nitric acid, hydroxymethyl propyl cellulose and glycerol in a kneader according to the mass ratio of 7:3:2:0.02:0.2:0.03, adding a proper amount of water, kneading into a plastic mixed contact body, putting the contact body into an extruder, extruding and molding under the conditions that the temperature is 25 ℃ and the pressure is 5MPa to prepare a square honeycomb hole blank, wherein the side lengths and the heights of four bottom edges of the square honeycomb hole blank are respectively 80cm and 100cm, and roasting the honeycomb blank for 2 hours under the air condition at 480 ℃ to obtain the flame-retardant honeycomb matrix D. Pt content of 460g/m per cubic honeycomb substrate3Ir content of 180g/m3The mass ratio of citric acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic honeycomb matrix is 40kg/m3The Fe content is 8kg/m3Preparing aqueous solution of cerium nitrate and ferric nitrate, soaking Pt and Ir solution on a honeycomb substrate, drying at 130 ℃ for 4 hours, further soaking Ce and Fe solution, and soaking the honeycomb substrate in 15 DEG CDrying again for 3 hours at 0 ℃, and roasting for 5 hours at 500 ℃ to obtain the flame-retardant porous matrix supported noble metal catalyst D1 with the surface area of 198m2g-1The most probable pore diameter is 5.7nm, and the pore volume is 0.47mlg-1The cross section of the honeycomb holes is 30mm2。
Example 5
Mixing attapulgite, kaolin, an SAPO molecular sieve, 65% mass concentration nitric acid, hydroxymethyl propyl cellulose, hexamethylene diamine and magnesium stearate in a mass ratio of 7:3:2:0.02:0.2: 0.01: stirring the mixture evenly in a kneader according to the proportion of 0.03, adding a proper amount of water, kneading the mixture into a plastic mixed contact body, putting the contact body into an extruder, extruding and molding the mixture under the conditions that the temperature is 25 ℃ and the pressure is 7MPa to prepare a square honeycomb hole green body, wherein the side length and the height of four bottom edges of the square honeycomb hole green body are respectively 80cm and 100cm, and roasting the honeycomb green body for 12 hours at the temperature of 500 ℃ under the air condition to obtain the flame-retardant honeycomb matrix E. The Pt content per cubic honeycomb substrate is 500g/m3The Pd content is 210g/m3The weight ratio of citric acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic honeycomb matrix is 40kg/m3Ni content of 11kg/m3Preparing aqueous solution of cerium nitrate and nickel nitrate, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking Ce and Ni solution, drying for 3 hours at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 480 ℃ to obtain the flame-retardant porous substrate supported noble metal catalyst E1 with the surface area of 186m2g-1The most probable pore diameter is 5.7nm, and the pore volume is 0.45mlg-1Honeycomb holes of 27mm2。
Example 6
The flame-retardant honeycomb substrate E of example 5 was used. The Pt content of each cubic honeycomb substrate is 500g/m3The Pd content is 200g/m3The mass ratio of citric acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic honeycomb matrix is 80kg/m3The Bi content is 11kg/m3Proportional arrangement ofSoaking Pt and Pd solution on a honeycomb substrate by using aqueous solution of cerium nitrate and bismuth nitrate, drying for 4 hours at the temperature of 130 ℃, further soaking Ce and Bi solution, drying for 3 hours at the temperature of 150 ℃, and roasting for 8 hours at the temperature of 500 ℃ to obtain the flame-retardant porous substrate supported noble metal catalyst F1 with the surface area of 182m2g-1The most probable pore diameter is 5.9nm, and the pore volume is 0.44mlg-1Honeycomb holes of 27mm2。
Example 7
The flame-retardant honeycomb substrate E of example 5 was used. The Pt content per cubic honeycomb substrate is 430g/m3Pd content of 150g/m3The mass ratio of citric acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic honeycomb matrix is 80kg/m3The Cr content is 20kg/m3Preparing aqueous solution of cerium nitrate and chromium nitrate according to the proportion, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking Ce and Cr solution, drying for 3 hours at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 500 ℃ to obtain the flame-retardant porous substrate supported noble metal catalyst G1 with the surface area of 198m2g-1The most probable pore diameter is 5.1nm, and the pore volume is 0.43mlg-1Honeycomb holes of 27mm2。
Example 8
The flame-retardant honeycomb substrate E of example 5 was used. The Pt content per cubic honeycomb substrate is 500g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the La content of each cubic honeycomb matrix is 80kg/m3Mn content of 20kg/m3Preparing aqueous solution of lanthanum nitrate and manganese nitrate, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking La and Mn solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 500 ℃ to obtain the flame-retardant porous substrate supported noble metal catalyst H1 with the surface area of 165m2g-1The most probable pore diameter is 6.3nm, pore volume of 0.42mlg-1Honeycomb holes of 27mm2。
Example 9
The flame-retardant honeycomb substrate E of example 5 was used. Pt content of 460g/m per cubic honeycomb substrate3The Pd content is 170g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the La content of each cubic honeycomb matrix is 80kg/m3Co content of 30kg/m3Preparing aqueous solution of lanthanum nitrate and cobalt nitrate according to the proportion, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking La and Co solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 3 hours at the temperature of 500 ℃ to obtain the flame-retardant porous substrate supported noble metal catalyst I1 with the surface area of 154m2g-1The most probable pore diameter is 6.3nm, and the pore volume is 0.42mlg-1Honeycomb holes of 27mm2。
Example 10
The flame-retardant honeycomb substrate E of example 5 was used. The Pt content per cubic honeycomb substrate is 480g/m3Pd content of 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the La content of each cubic honeycomb matrix is 90kg/m3The Fe content is 18kg/m3Preparing aqueous solution of lanthanum nitrate and ferric nitrate, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking La and Fe solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 3 hours at the temperature of 500 ℃ to obtain the flame-retardant porous substrate supported noble metal catalyst J1 with the surface area of 154m2g-1The most probable pore diameter is 6.6nm, and the pore volume is 0.43mlg-1Honeycomb holes of 27mm2。
Example 11
The flame-retardant honeycomb substrate E of example 5 was taken. The Pt content of each cubic honeycomb substrate is 480g/m3The Pd content is 200g/m3The mass ratio of the hydrochloric acid to the chloroplatinic acid is that of the chloroplatinic acid solution and the hydrochloric acid aqueous solution of the palladium chlorideThe quantity ratio is 3:1, and the La content of each cubic honeycomb matrix is 90kg/m3Ni content of 20kg/m3Preparing aqueous solution of lanthanum nitrate and nickel nitrate, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking La and Ni solution, drying for 3 hours at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 490 ℃ to obtain the flame-retardant porous substrate supported noble metal catalyst K1 with the surface area of 160m2g-1The most probable pore diameter is 6.7nm, and the pore volume is 0.40mlg-1Honeycomb holes of 27mm2。
Example 12
The flame-retardant honeycomb substrate E of example 5 was used. The Pt content per cubic honeycomb substrate is 490g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the La content of each cubic honeycomb matrix is 90kg/m3And a Bi content of 20kg/m3Preparing aqueous solution of lanthanum nitrate and bismuth nitrate, firstly dipping Pt and Pd solution on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further dipping La and Bi solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 3 hours at the temperature of 500 ℃ to obtain the flame-retardant porous matrix supported noble metal catalyst L1 with the surface area of 157m2g-1The most probable pore diameter is 6.3nm, and the pore volume is 0.39mlg-1Honeycomb holes of 27mm2。
Example 13
The flame-retardant honeycomb substrate E of example 5 was used. The Pt content per cubic honeycomb substrate is 480g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the La content of each cubic honeycomb matrix is 90kg/m3Preparing lanthanum nitrate aqueous solution according to the proportion, firstly dipping Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further dipping La solution, drying for 3 hours again at the temperature of 180 ℃, and roasting for 5 hours at the temperature of 450 ℃ to obtain the flame-retardant porous substrate supported noble metal catalyst M1, wherein the surface of the flame-retardant porous substrate supported noble metal catalyst M1Product of 180m2g-1The most probable pore diameter is 5.7nm, and the pore volume is 0.46mlg-1The cross section of the honeycomb holes is 27mm2。
Example 14
The flame-retardant honeycomb substrate E of example 5 was used. The Pt content per cubic honeycomb substrate is 480g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic honeycomb matrix is 90kg/m3The preparation method comprises the steps of preparing a cerium nitrate aqueous solution, firstly soaking Pt and Pd solutions on a honeycomb substrate, drying at the temperature of 130 ℃ for 4 hours, then further soaking the Ce solution, drying at the temperature of 180 ℃ for 3 hours again, and roasting at the temperature of 500 ℃ for 2 hours to obtain the flame-retardant porous substrate supported noble metal catalyst N1 with the surface area of 163m2g-1The most probable pore diameter is 6.5nm, and the pore volume is 0.43mlg-1The cross section of the honeycomb holes is 27mm2。
Example 15
The flame-retardant honeycomb substrate E of example 5 was used. The Pt content per cubic honeycomb substrate is 480g/m3Pd content of 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the Cr content of each cubic honeycomb matrix is 90kg/m3Mo content of 20kg/m3Preparing aqueous solution of chromium nitrate and ammonium molybdate according to the proportion, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking Cr and Mo solution, drying for 3 hours again at the temperature of 180 ℃, and roasting for 4 hours at the temperature of 550 ℃ to obtain the flame-retardant porous substrate supported noble metal catalyst O1 with the surface area of 127m2g-1The most probable pore diameter is 8.2nm, and the pore volume is 0.26mlg-1The cross section of the honeycomb holes is 27mm2。
Example 16
The flame-retardant honeycomb substrate E of example 5 was used. The Pt content per cubic honeycomb substrate is 480g/m3The Pd content is 150g/m3The ratio of the chloroplatinic acid solution to the hydrochloric acid solution of the palladium chloride is preparedThe mass ratio of the hydrochloric acid to the chloroplatinic acid is 3:1, and the content of K in each cubic honeycomb matrix is 10kg/m3Re content of 30kg/m3W content of 20kg/m3Preparing aqueous solution of potassium nitrate, rhenium chloride and ammonium tungstate, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking solution of K, Re and W, drying again for 3 hours at the temperature of 180 ℃, and roasting for 4 hours at the temperature of 480 ℃ to obtain the flame-retardant porous substrate supported noble metal catalyst P1 with the surface area of 140m2g-1The most probable pore diameter is 7.3nm, and the pore volume is 0.33mlg-1The cross section of the honeycomb holes is 27mm2。
Example 17
Kaolin, a 13X molecular sieve, 65% mass concentration nitric acid, methylcellulose and magnesium stearate are mixed according to the mass ratio of 10: 5: 0.02:0.2: stirring the mixture evenly in a kneader according to the proportion of 0.001, adding a proper amount of water, kneading the mixture into a plastic mixed contact body, putting the contact body into an extruder, extruding and molding the mixture under the conditions of the temperature of 25 ℃ and the pressure of 5MPa to prepare a blank of a square honeycomb hole, wherein the side length and the height of four bottom edges of the blank of the square honeycomb hole are respectively 80cm and 100cm, and roasting the honeycomb blank for 4 hours at the temperature of 500 ℃ under the air condition to obtain the flame-retardant honeycomb matrix Q. The Pt content per cubic honeycomb substrate is 400g/m3Pd content of 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic honeycomb matrix is 90kg/m3Mn content of 20kg/m3Preparing aqueous solution of cerium nitrate and manganese nitrate, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking Ce and Mn solution, drying for 3 hours again at the temperature of 180 ℃, and roasting for 4 hours at the temperature of 550 ℃ to obtain the flame-retardant porous substrate supported noble metal catalyst Q1 with the surface area of 154m2·g-1The most probable pore diameter was 7.4nm, and the pore volume was 0.41 ml/g-1The area of the honeycomb holes is 9.1mm2。
Example 18
Mixing attapulgiteThe soil, the silicon dioxide, the nitric acid with the mass concentration of 65%, the hydroxymethyl propyl cellulose and the glycerol are mixed according to the mass ratio of 10: 4: 0.02:0.2: 0.001, stirring uniformly in a kneading machine, adding a proper amount of water, kneading into a plastic mixed contact body, putting the contact body into an extruder, extruding and molding under the conditions of 25 ℃ and 5MPa to prepare a blank of square honeycomb holes, wherein the side length and the height of four bottom edges of the blank of the square honeycomb holes are respectively 80cm and 100cm, and the honeycomb blank is roasted in the air at 500 ℃ for 2 hours to obtain the flame-retardant honeycomb matrix R. The Pt content per cubic honeycomb substrate is 430g/m3The Ru content is 170g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of ruthenium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic honeycomb matrix is 70kg/m3The Cr content is 30kg/m3Preparing aqueous solution of cerium nitrate and chromium nitrate, firstly dipping Pt and Ru solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further dipping Ce and Cr solution, drying for 3 hours again at the temperature of 180 ℃, and roasting for 4 hours at the temperature of 550 ℃ to obtain the flame-retardant porous substrate supported noble metal catalyst R1 with the surface area of 231m2·g-1The most probable pore diameter is 8.2nm, and the pore volume is 0.53 ml/g-1The area of the honeycomb holes is 9.2mm2。
Example 19
Mixing attapulgite, alumina, titanium oxide, 65% nitric acid, hydroxymethyl propyl cellulose and glycerol according to a mass ratio of 10: 3: 1: 0.02:0.2: stirring the mixture evenly in a kneader according to the proportion of 0.001, adding a proper amount of water, kneading the mixture into a plastic mixed contact body, putting the contact body into an extruder, extruding and molding the mixture under the conditions that the temperature is 25 ℃ and the pressure is 5MPa to prepare a blank of square honeycomb holes, wherein the side lengths and the heights of four bottom edges of the blank of the square honeycomb holes are 80cm and 100cm respectively, and roasting the blank of the honeycomb in the air at the temperature of 500 ℃ for 2 hours to obtain the flame-retardant honeycomb matrix S. The Pt content per cubic honeycomb substrate is 300g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and each cubic honeycomb matrixThe Ce content is 50kg/m3Ni content of 40kg/m3Preparing aqueous solution of cerium nitrate and nickel nitrate, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking Ce and Ni solution, drying for 3 hours at the temperature of 180 ℃, and roasting for 4 hours at the temperature of 550 ℃ to obtain the flame-retardant porous substrate supported noble metal catalyst S1 with the surface area of 196m2·g-1The most probable pore diameter was 8.4 nm, and the pore volume was 0.49 ml/g-1The area of the honeycomb holes is 9.4mm2。
Comparative example 1
Mixing alumina, titanium oxide, 65% nitric acid, hydroxymethyl propyl cellulose and glycerol according to a mass ratio of 3: 1: 0.02:0.2: stirring the mixture evenly in a kneader according to the proportion of 0.001, adding a proper amount of water, kneading the mixture into a plastic mixed contact body, putting the contact body into an extruder, extruding and molding the mixture under the conditions that the temperature is 25 ℃ and the pressure is 5MPa to prepare a blank of square honeycomb holes, wherein the side lengths and the heights of four bottom edges of the blank of the square honeycomb holes are 80cm and 100cm respectively, and roasting the blank of the honeycomb in the air at the temperature of 500 ℃ for 2 hours to obtain the flame-retardant honeycomb matrix T. The Pt content of each cubic honeycomb substrate is 300g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic honeycomb matrix is 50kg/m3Ni content of 40kg/m3Preparing aqueous solution of cerium nitrate and nickel nitrate, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking Ce and Ni solution, drying for 3 hours at the temperature of 180 ℃, and roasting for 4 hours at the temperature of 550 ℃ to obtain the flame-retardant porous substrate supported noble metal catalyst T1 with the surface area of 147m2·g-1The most probable pore diameter was 7.4nm, and the pore volume was 0.42ml g-1The area of the honeycomb holes is 8.6mm2。
Example 20
The flame-retardant porous matrix noble metal-supported catalysts of examples 1 to 19 and the catalyst of comparative example 1 were placed in a fixed bed reactor, and non-methane total hydrocarbons were fedIs 1200mg/m3The VOCs gas (mixture of mixed C-octaarene and mixed C-tetra alkane) is reacted at the temperature of 350 ℃ and the space velocity of 10000h-1The reaction was carried out under the conditions described above, and the results of the detection of VOCs at the outlet by gas chromatography are shown in Table 1.
TABLE 1 comparison of reactivity of flame-retardant type catalyst with noble metal supported on porous substrate
| Catalyst and process for preparing same | The reaction time is 1h, and the concentration (mg/m) of VOCs at the outlet is3） | The reaction time is 500h, and the concentration (mg/m) of VOCs at the outlet is3） | The reaction is carried out for 1000h, and the concentration (mg/m) of VOCs at the outlet is3） |
| A1 | 12.1 | 13.4 | 14.7 |
| B1 | 2.2 | 2.3 | 3.1 |
| C1 | 4.2 | 4.5 | 5.2 |
| D1 | 6.1 | 6.6 | 7.2 |
| E1 | 5.7 | 6.3 | 7.2 |
| F1 | 4.8 | 5.1 | 5.5 |
| G1 | 4.8 | 5.5 | 6.1 |
| H1 | 6.3 | 6.8 | 7.4 |
| I1 | 7.1 | 7.8 | 8.6 |
| J1 | 7.4 | 8.1 | 8.8 |
| K1 | 6.8 | 7.4 | 8.1 |
| L1 | 6.3 | 7.2 | 7.7 |
| M1 | 11.4 | 12.2 | 14.7 |
| N1 | 14.1 | 15.7 | 17.9 |
| O1 | 12.2 | 14.3 | 16.7 |
| P1 | 13.3 | 15.4 | 17.8 |
| Q1 | 3.7 | 4.1 | 4.4 |
| R1 | 6.9 | 7.3 | 7.8 |
| S1 | 9.1 | 9.5 | 10.1 |
| T1 | 24.2 | 26.1 | 27.9 |
Example 20
The catalyst of example 2 was subjected to elemental analysis of metals, and a sample obtained after 1000 hours of the above reaction of treating the VOCs gas was subjected to elemental analysis, in terms of the metal content per volume of the porous substrate, as shown in table 2.
TABLE 2 analysis of key elements after catalytic reaction of flame-retardant porous matrix supported noble metal catalyst
Example 21
The flame-retardant porous matrix supported noble metal catalyst in the example 19 and the catalyst in the comparative example 1 are respectively loaded into a fixed bed reactor, acrylic acid-containing wastewater with COD of 35000mg/L is introduced, and the airspeed of the wastewater is 0.5h-1The reaction temperature was 260 ℃ and the pressure was 5MPa, and the COD of the effluent at the reaction outlet after 100 hours and the results of the analysis of the contents of the catalyst elements before and after the reaction are shown in Table 3.
TABLE 3 comparison of the reaction between the flame-retardant porous matrix supported noble metal catalyst
As can be seen from table 3, the porous matrix-supported catalyst of the present invention exhibited excellent catalytic oxidation performance for wastewater. In the porous substrate-supported catalyst of the present invention, the active metal component is firmly supported on the porous substrate, and the active metal component is hard to fall off even if it is washed with water for a long time.
Although the invention is described in detail herein with reference to exemplary embodiments, it should be understood that the invention is not limited to the described embodiments. Those having ordinary skill in the art and access to the teachings herein will recognize additional variations, modifications, and embodiments within the scope thereof. Accordingly, the invention is to be broadly construed, consistent with the claims which are appended hereto.
Claims (17)
1. A noble metal catalyst loaded on a flame-retardant porous matrix is characterized by comprising the flame-retardant porous matrix, noble metal and component components loaded on the flame-retardant porous matrix,
wherein the noble metal is at least one element selected from Pt, Pd, Ru, Rh, Au, Ir and Ag, preferably at least one combination selected from the combination of Pt and Pd, the combination of Pt and Ru, the combination of Pt and Au and the combination of Pt and Ir,
the additive component is at least one selected from the group A elements, the additive is preferably selected from at least one combination of Ce and Mo, Ce and Mn, Ce and Co, Ce and Fe, Ce and Ni, Ce and Bi, Ce and Cr, La and Mn, La and Fe, La and Co, La and Ni, La and Bi,
group A: li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce;
based on the total volume of the flame-retardant porous matrix supported noble metal catalyst, the content of noble metal (calculated by noble metal simple substance) is 100-1300 g/m3Preferably 150 to 1000 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200kg/m3Preferably 15 to 150 kg/m3，
The flame-retardant porous matrix comprises at least one original matrix selected from attapulgite and kaolin and at least one inorganic material selected from inorganic porous solids, wherein the content of the original matrix is 10-99.5 mass%, preferably 20-99 mass%, and the content of the inorganic material is 0.5-90 mass%, preferably 1-80 mass%, more preferably 5-80 mass%, even more preferably 8-70 mass%, and even more preferably the balance, based on the total mass of the porous matrix.
2. The catalyst according to claim 1, wherein the catalyst consists essentially of the flame retardant porous substrate, the at least one noble metal supported on the porous substrate, and the module component, preferably the catalyst consists only of the flame retardant porous substrate, the at least one noble metal supported on the porous substrate, and the module component.
3. The catalyst according to claim 1 or 2, wherein the BET specific surface area of the catalyst is 100 to 800m2·g-1Preferably 110 to 800m2·g-1The most probable pore diameter is 2 to 16nm, preferably 4 to 12nm, and the pore volume is 0.15 to 1.0 ml/g-1Preferably 0.2 to 1.0 ml/g-1。
4. The catalyst of any one of claims 1-3, wherein the inorganic material is at least one selected from the group consisting of silica, alumina, magnesia, silica alumina, magnesia alumina, titania silica, titania, molecular sieves, and montmorillonite.
5. Catalyst according to any of claims 1 to 4, shaped into shaped bodies having the appearance of spheres, cubes, cuboids, cylinders or raschig rings, preferably having one or more of a circular, square, triangular, hexagonal or rhombic structure of macrocells, preferably the individual macrocells have a cross-sectional area of 1mm2~80mm2Preferably 1mm2~35mm2The thickness of the hole wall is 1-4 mm, preferably 1-2.5 mm.
6. The catalyst according to any one of claims 1 to 5, wherein the positive pressure strength of the catalyst is 2 to 8MPa, preferably 2 to 6MPa, and the side pressure strength is 0.1 to 2MPa, preferably 0.2 to 2 MPa.
7. The preparation method of the flame-retardant noble metal catalyst loaded on the porous matrix is characterized by comprising the following steps:
(1) mixing and contacting at least one original matrix selected from attapulgite and kaolin, at least one inorganic material selected from inorganic porous solids, peptizing agent and water to prepare a plastic mixed contact body; wherein the content of the original matrix is 10 to 99.5 mass%, preferably 20 to 99 mass%, and the content of the inorganic material is 0.5 to 90 mass%, preferably 1 to 80 mass%, more preferably 5 to 80 mass%, further preferably 8 to 70 mass%, and further preferably the balance, with respect to the total amount of the original matrix and the inorganic material;
(2) optionally, molding the plastic mixed contact body to obtain a porous matrix blank;
(3) roasting the mixed contact body obtained in the step (1) or the porous matrix blank obtained in the step (2) to obtain a flame-retardant porous matrix;
(4) contacting a solution or suspension of a precursor of at least one precious metal component and a solution or suspension of a precursor of at least one auxiliary component with the flame-retardant porous matrix to obtain a contact product; and
(5) and roasting the contact product to obtain the flame-retardant porous matrix supported catalyst.
8. The production method according to claim 7, wherein the peptizing agent is at least one selected from the group consisting of inorganic acids, inorganic bases, polycarboxylic acids, monohydric alcohols, polyhydric alcohols, polyamines, cellulose derivatives, and carboxylic acid salts, preferably at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, sodium hydroxide, calcium hydroxide, potassium hydroxide, magnesium hydroxide, lithium hydroxide, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, pentaerythritol, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, methylcellulose, hydroxymethylcellulose, hydroxymethylpropylcellulose, carboxymethylcellulose, magnesium stearate, and sodium stearate.
9. The production method according to claim 7 or 8, wherein in the step (2), the molding is performed at a temperature of 20 to 80 ℃ under a pressure of 0.5 to 8MPa, preferably 1 to 6 MPa.
10. The production method according to any one of claims 7 to 9, wherein the calcination temperature in the step (3) is 200 to 580 ℃, preferably 200 to 550 ℃, and more preferably 300 to 550 ℃.
11. The production method according to any one of claims 7 to 10, further comprising, before the step (3), a step of subjecting the plastic hybrid contact body in the step (1) or the porous base body in the step (2) to a heat treatment at a temperature of 20 to 150 ℃, preferably 30 to 120 ℃, more preferably 50 to 100 ℃.
12. The production method according to any one of claims 7 to 11, wherein the auxiliary component is at least one selected from the group A elements, the auxiliary is preferably at least one selected from the group consisting of a combination of Ce and Mo, a combination of Ce and Mn, a combination of Ce and Co, a combination of Ce and Fe, a combination of Ce and Ni, a combination of Ce and Bi, a combination of Ce and Cr, a combination of La and Mn, a combination of La and Fe, a combination of La and Co, a combination of La and Ni, a combination of La and Bi,
group A: li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce,
the noble metal is at least one selected from Pt, Pd, Ru, Rh, Au, Ir and Ag, preferably at least one selected from Pt and Pd combination, Pt and Ru combination, Pt and Au combination and Pt and Ir combination,
the precursor of the noble metal is soluble salt and/or acid of the noble metal, preferably at least one selected from chloride, nitrate, acetate, sulfate and ammonium salt, and further preferably at least one selected from palladium chloride, palladium nitrate, palladium acetate, dichlorodiammine palladium, chloroplatinic acid, platinum chloride, dinitrosopropylamine and dichlorotetrammonium;
the precursor of the auxiliary component is at least one of chloride, nitrate, acetate, sulfate, ammonia salt and phosphate of the auxiliary component,
in the obtained catalyst, based on the total volume of the catalyst, the content of the noble metal (calculated by a noble metal simple substance) is 100-1300 g/m3Preferably 150 to 1000 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200kg/m3Preferably 15 to 150 kg/m3。
13. The production method according to any one of claims 7 to 12, wherein at least one of a complexing agent, a stabilizer, and a pH adjuster may be added to the solution or suspension of the precursor of the noble metal component and/or the solution or suspension of the precursor of the auxiliary component.
14. Use of the flame-retardant porous substrate-supported catalyst according to any one of claims 1 to 6 or the flame-retardant porous substrate-supported catalyst prepared by the preparation method according to any one of claims 7 to 13, for catalytic oxidation of volatile organic compounds.
15. Use according to claim 14, wherein the conditions for the catalytic oxidation of volatile organic compounds are: the gas containing volatile organic compounds is enabled to have a gas volume space velocity of 4000-25000 h-1And contacting the porous matrix supported catalyst at the temperature of 150-450 ℃.
16. Use of the flame retardant porous substrate-supported catalyst according to any one of claims 1 to 6 or the flame retardant porous substrate-supported catalyst prepared by the preparation method according to any one of claims 7 to 13 for catalytically oxidizing wastewater to reduce COD.
17. Use according to claim 16, wherein said conditions are: the space velocity of the liquid volume of the wastewater is 0.2 to 3h-1The pressure is 2-8MPa, and the reaction temperature is 200-280 ℃.
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