CN103131488A - Low-concentration methane catalytic combustion catalyst and preparation method of the same - Google Patents
Low-concentration methane catalytic combustion catalyst and preparation method of the same Download PDFInfo
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Abstract
The invention provides a low-concentration methane catalytic combustion catalyst and a preparation method of the low-concentration methane catalytic combustion catalyst. The low-concentration methane catalytic combustion catalyst comprises a catalytic activity component, a catalyst carrier of Al2O3 and a metal oxide co-carrier. One kind or several kinds of the combination of platinum family precious metal of palladium (Pd), platinum (Pt), ruthenium (Ru), iridium (Ir) and rhodium (Rh) are used as the catalytic activity component; at least one kind in metal oxide of magnesium (Mg), lanthanum (La), ferrum (Fe), manganese (Mn), nickel (Ni), cobalt (Co), chromium (Cr) and calcium (Ca) is used as the metal oxide co-carrier. Arbitrary one kind of the methods of an impregnation method, a homogeneous precipitation method, a co-precipitation method and a pyrolytic method is used for preparing a catalyst precursor. Then the catalyst is formed after being filtered, washed, dried, roasted, formed, roasted again and restored. The low-concentration methane catalytic combustion catalyst and the preparation method of the low-concentration methane catalytic combustion catalyst have the advantages of being capable of stably combusting under the lean-burn, oxygen-enriched and high-water-vapor conditions, high in activity, long in service life and the like.
Description
Technical field
The invention belongs to methane and low-carbon (LC) hydro carbons combustioncatalysts field, be specifically related to a kind of Catalysts and its preparation method of low-concentration methane catalyticcombustion.
Background technology
Coal-seam gas is a kind of attached hydrocarbon gas that is stored in the coal seam, as rationally not utilizing, not only can cause huge energy dissipation, also can cause significant Greenhouse effect.In the coal mining process, mainly discharge the coal-seam gas of three types: CMM (Coal Mine Methane), CBM (Coalbed Methane), VAM (Ventilation Air Methane).Wherein account for the mine ventilation gas (VAM) of coal-seam gas methane content 70%, due to the large (100-500m of gas flow
3/ s), methane concentration low (0.2-1.0vol%) and the characteristics such as unstable, also there is no the ripe technology of utilizing at present.Although some companies develop ventilating gas indirect utilization technology both at home and abroad, limited by region and Technical Economy, fail to realize industrialization; Ventilating gas also can adopt flow-reversal technique directly to utilize by thermal insulation or catalyticcombustion, and as the VOCSIDIZER system of U.S. MEGTEC company exploitation, owing to adopting the adiabatic combustion principle, temperature of combustion is up to 1300
oC may produce NO
X, carrying out at present Industry Promotion; And the employing catalyticcombustion can effectively avoid the harshness to reactor material that the high-temperature heat insulation burning causes to require and NO
XGeneration, still, under oxygen-enriched atmosphere, the exploitation of methyl hydride combustion catalyst is the technical bottleneck that realizes that the lower concentration ventilating gas is effectively administered.Particularly, the water that the saturation water in the ventilating gas exhaust system and burning generate, stability that all can the remarkably influenced combustioncatalysts.Research finds that water can be adsorbed on catalyst surface, and does not have activated oxyhydroxide with active ingredient reaction generation, has hindered active sites.Burch(R. Burch, D. J. Crittle and M. J. Hayes, Catal. Today 1999 47:229-234) thinks that the decomposition of the oxyhydroxide that the reaction of water and active ingredient generates and the fracture of OH key are the control steps of methyl hydride combustion reaction.So the key that the low-concentration methane catalytic combustion technology is used is that to have higher methyl hydride combustion under a kind of high water content of exploitation, oxygen-enriched atmosphere active, and the methyl hydride combustion catalyst of withstand high temperatures hydro-thermal operating mode over a long time.
The catalyzer of precious metals pd, Pt, Rh, Au etc. is to study at present a more class methyl hydride combustion catalyst, compares with other catalyzer, and precious metal demonstrates good low temperature ignition activity and catalytic activity.The high reactivity of precious metal comes from the atom pairs O of metallic state-O, C-H key stronger activation capacity, makes originally very stable molecule form the extremely strong free radical of reactivity worth, thereby triggers chain reaction.The factor that affects catalyst performance has specific surface area, crystalline structure and the crystal degree of scatter on carrier etc.The inactivation of catalyzer in reaction process may be crystal conversion, specific surface area reduces and the coefficient results of factor such as carrier and active ingredient generation strong interaction.Studies show that, kind of carrier has a strong impact on catalyst activity, and the carrier that is used for the combustion of methane catalyzer has Al
2O
3, SiO
2, CeO
2, ZrO
2, TiO
2And composite oxides etc., wherein that the most frequently used is Al
2O
3In order to improve catalyst performance, people continue Al again
2O
3Carrier carries out modification, as adding auxiliary agent or common carrier, as Ce
xZr
1-xO
2,, Ni, Co, La, Nd, Mg etc. are in the hope of improving the performance of catalyzer.Document (Y. Ozawa, Y. Tochihara, M. Nagai, S. Omi, Catal Commun 2003 4:87-90) shows that adding of La or Nd can stable carrier, reduces catalyst deactivation.Thevenin etc. (P.O. Thevenin, A. Alcalde, L.J. Pettersson, S.G. Jaras, J.L.G. Fierro, J Catal 2003 215:78-86.) adds CeO in the alumina supporter that is mixed with La and/or Ba auxiliary agent
2, find CeO
2Interpolation improved the activity of catalyzer.Eguchi and Sekizawa(K. Sekizawa, K. Eguchi, H. Widjaja, M. Machida, H. Arai, Catal Today 1996 28:245-250) etc. has studied interpolation Co, Cr, Cu, Fe, the PdO/Al of the metal oxides such as Mn or Ni
2O
3Catalyzer is found the raising that helps catalyst activity that adds of a large amount of NiO.
But at present, the hydrothermal stability problem of low-concentration methane catalyst for catalytic combustion is not well solved yet, and the related data of stability also seldom.
Summary of the invention
The purpose of this invention is to provide a kind of low-concentration methane catalyst for catalytic combustion and preparation method thereof, this catalyzer can stable burning under fuel-sean oxygen enrichment, high water vapour atmosphere, active high, the life-span is long.
The invention provides a kind of low-concentration methane catalyst for catalytic combustion, comprise catalytic active component, support of the catalyst Al
2O
3And metal oxide is total to carrier, catalytic active component is selected from one or more the combination in platinum family precious metal palladium Pd, platinum Pt, ruthenium Ru, iridium Ir, rhodium Rh, and metal oxide carrier altogether is at least a in magnesium Mg, lanthanum La, iron Fe, manganese Mn, nickel, cobalt Co, chromium Cr, calcium Ca metal oxide.
Catalyzer provided by the invention, described catalytic active component are a kind of in Pd, Pd-Pt, Pd-Rh, Pd-Pt-Rh.
Catalyzer provided by the invention, described in precious metal simple substance, the 0.01-5%(that the content of catalytic active component accounts for the catalyzer total mass is preferably 0.1-2%); In simple substance, the 10-100%(that the content of Pd accounts for catalytic active component is preferably 60-100%).
Catalyzer provided by the invention, described metal oxide is total to the 5-45% that carrier accounts for the catalyzer total mass.
The present invention also provides the preparation method of described catalyzer, and concrete steps are as follows: (1) Al
2O
3Carrier and metal oxide are total to any one method in carrier employing pickling process, homogeneous precipitation method, coprecipitation method, thermal decomposition method, are prepared into Binary Mixtures or mixture, and drying and roasting obtain catalyst precursor; (2) catalytic active component is supported on the catalyst precursor that above-mentioned steps (1) obtains, oxidized catalyst is made in drying and roasting; (3) oxidized catalyst is reduced, get final catalyzer.
Method for preparing catalyst provided by the invention, described pickling process is dissolved in deionized water for metal oxide is total to the corresponding metallic cation of carrier, with Al
2O
3Carrier immerses this solution, makes mixture, then with the mixture of gained under 100-150 ℃ dry 10-30 hour, 500-1300 ℃ lower roasting 1-4 hour; This step can repeat until obtain needed loading, and get final product.
Method for preparing catalyst provided by the invention, described coprecipitation method are with Al
2O
3Carrier and the metal oxide corresponding metallic cation of carrier altogether are dissolved in deionized water, make the solution of water-soluble salt; Under the condition of vigorous stirring, with finite concentration ammoniacal liquor NH
3H
2O, sodium carbonate Na
2CO
3, sodium bicarbonate NaHCO
3In a kind of slow release type alkaline solution add in the solution of above-mentioned water-soluble salt, with Al
2O
3Carrier and metal oxide be the corresponding metallic cation precipitation of carrier altogether, at 0-150 ℃ of ageing 1-10 hour, obtain containing suspension or the slurry of precipitation, then suspension or slurry are carried out solid-liquid separation, be precipitated solid, moulding, under 100-150 ℃ dry 10-30 hour, 500-1300 ℃ lower roasting 1-4 hour, and get final product.
Method for preparing catalyst provided by the invention, described catalyst precursor are one or more in Palladous chloride, platinum chloride, Palladous nitrate, platinum nitrate, ruthenium chloride, rhodium chloride, Yttrium trichloride, palladium sponge, spongy platinum.
Method for preparing catalyst provided by the invention, the Aging Temperature in described coprecipitation method are 40-120 ℃ (being preferably 80-110 ℃), and digestion time is 5-8 hour.
Method for preparing catalyst provided by the invention, the maturing temperature in described pickling process and coprecipitation method are 700-1200 ℃ (being preferably 900-1100 ℃).
Method for preparing catalyst provided by the invention, described step (2) is for to adopt equi-volume impregnating to be supported on catalyst precursor catalytic active component, then under 100-150 ℃ dry 10-30 hour, 200-600 ℃ (being preferably 200-400 ℃) lower roasting 1-4 hour; This step can repeat namely to get oxidized catalyst until obtain needed loading.
In method for preparing catalyst provided by the invention, described step (3), the reduction mode of oxidized catalyst is 10-100%H
2, all the other are N
2Under atmosphere in 400-500 ℃ of reductase 12-4 hour.
Catalyzer provided by the invention is applied to administer or the coal-seam gas catalytic deoxidation is administered methane catalytic combustion process or other hydrocarbon oxidation catalyst subtractive processs as purpose take mine ventilation gas.
Catalyzer of the present invention should have following characteristic: can stable burning under the rich combustion gas atmosphere of fuel-sean oxygen rich air atmosphere or oxygen deprivation, active high, the life-span is long etc.Wherein, can be under fuel-sean oxygen rich air atmosphere long-time high reactivity burning is one of most critical place of the catalyzer that the present invention relates to and catalyticcombustion technique.
Catalyzer for the low-concentration methane catalyticcombustion provided by the invention is the longevity test more than 3000 hours in the laboratory, CH
4Transformation efficiency maintains more than 90% all the time.By introduce carrier altogether in catalyst system, utilize the interaction of itself and precious metal, both improved the stability of carrier, improved again dispersity and the stability of active ingredient on carrier.Reduce before catalyzer is used, the gained catalyzer not only can improve the stability of combustion processes, and its low-temperature ignition starting performance can obtain lifting by a relatively large margin simultaneously.
Catalyzer provided by the invention efficiently solves the poor problem of catalyzer hydrothermal stability in the low-concentration methane catalyticing combustion process, and method for preparing catalyst is simple, can carry out large-scale industrial production.
Description of drawings
Fig. 1 is the hydrothermally stable linearity curve of catalyzer K of the present invention, (unstripped gas is methane, air, water vapor, and wherein the methane volume fraction is 0.4%, air balance (butt composition); In unstripped gas, the water vapor volume fraction is 4%; The unstripped gas air speed is 80000h
-1(butt air speed), normal pressure, temperature of reaction is 600 ℃.）。
Embodiment
Following examples will be further described the present invention, but not thereby limiting the invention.
Reaction velocity of the present invention is defined as reactor feed gas (butt) and per hour enters the standard volume flow of reactive system divided by the volume of catalyzer.Represent with GHSV, unit is h
-1
CH of the present invention
4Transformation efficiency is defined as CH in unstripped gas
4The molar percentage that is converted, i.e. CH in unstripped gas and gas product
4The difference of mole number with respect to CH in unstripped gas
4Molar percentage, unit is %.
Embodiment 1: catalyst A: 0.47%Pd/ 6.2%MgO/Al
2
O
3
(1) take 16.10g MgCl
26H
2O adds deionized water dissolving to 20mL;
(2) with 38g Al
2O
3Particle immerses in the aqueous solution of step (1) configuration, and under 120 ℃ dry 10 hours, 900 ℃ of lower roastings 3 hours namely got catalyst precursor;
(3) catalyst precursor that step (2) is made immerses the Pd (NO3) that 20mL contains 9.6mg/mL Pd
2Solution, under 120 ℃ dry 10 hours, 200 ℃ of lower roastings 2 hours obtained required oxidation state noble metal catalyst;
(4) the catalyzer 10%H that step (3) is made
2-90%N
2Under mixed gas and 400 ℃, reduction is 3 hours, obtains precious metal simple substance attitude catalyzer, and catalyst components is 0.47%Pd/ 6.2%MgO/Al
2O
3
Embodiment 2: catalyst B: 0.96%Pd/ 8.9%La
2
O
3
/ Al
2
O
3
(1) take 7.50g La (NO
3)
36H
2O adds deionized water dissolving to 25mL;
(2) with 48g Al
2O
3Particle immerses in the aqueous solution of step (1) configuration, and under 105 ℃ dry 15 hours, 1000 ℃ of lower roastings 3 hours namely got catalyst precursor;
(3) catalyst precursor that step (2) is made immerses the Pd (NO that 26.4mL contains 20.5mg/mL Pd
3)
2Solution, under 105 ℃ dry 15 hours, 250 ℃ of lower roastings 3 hours obtained required oxidation state noble metal catalyst;
(4) the catalyzer 20%H that step (3) is made
2-80%N
2Mixed gas and 420 ℃ lower reductase 12 .5 hour obtain precious metal simple substance attitude catalyzer, and catalyst components is 0.96%Pd/ 8.9%La
2O
3/ Al
2O
3
Embodiment 3: catalyzer C:0.39%Pd/ 9.6%CoO/Al
2
O
3
(1) take 11.89g Co (NO
3)
36H
2O adds deionized water dissolving to 15mL;
(2) with 28.8g Al
2O
3Particle immerses in the aqueous solution of step (1) configuration, and under 110 ℃ dry 30 hours, 1000 ℃ of lower roastings 3 hours namely got catalyst precursor;
(3) catalyst precursor that step (2) is made immerses the PdCl that 15.9mL contains 7.8mg/mL Pd
2Solution, under 110 ℃ dry 30 hours, 210 ℃ of lower roastings were after 2 hours, washed Cl in catalyzer off with deionized water
-, then under 110 ℃ dry 30 hours, obtain required oxidation state noble metal catalyst;
(4) the catalyzer 10%H that step (3) is made
2-90%N
2Under mixed gas and 400 ℃, reduction is 3 hours, obtains precious metal simple substance attitude catalyzer, and catalyst components is 0.39%Pd/ 9.6%CoO/Al
2O
3
Embodiment 4: catalyzer D:0.81%Pd/0.06%Pt/0.08%Rh/ 7.7%CoO/Al
2
O
3
(1) take 15.62g Co (NO
3)
36H
2O adds deionized water dissolving to 25mL;
(2) with 48g Al
2O
3Particle immerses in the aqueous solution of step (1) configuration, and under 110 ℃ dry 20 hours, 1100 ℃ of lower roastings 3 hours namely got catalyst precursor;
(3) catalyst precursor that step (2) is made immerses 26.1mL and contains 16.2mg/mL Pd, 1.3mg/mL Pt, the PdCl of 1.7mg/mL Rh
2,, PtCl
2, RhCl
2Mixing solutions, under 130 ℃ dry 20 hours, 250 ℃ of lower roastings were after 3 hours, washed Cl in catalyzer off with deionized water
-, then under 130 ℃ dry 20 hours, obtain required oxidation state noble metal catalyst;
(4) the catalyzer 5%H that step (3) is made
2-95%N
2Mixed gas and 400 ℃ lower reductase 12 .5 hour obtain precious metal simple substance attitude catalyzer, and catalyst components is 0.81%Pd/0.06%Pt/0.08%Rh/ 7.7%CoO/Al
2O
3
Embodiment 5: catalyzer E:0.85%Pd/0.09%Pt/10.6%Fe
2
O
3
/ Al
2
O
3
(1) take 17.40g Fe (NO
3)
39H
2O adds deionized water dissolving to 15mL;
(2) with 28.8g Al
2O
3Particle immerses in the aqueous solution of step (1) configuration, and under 120 ℃ dry 10 hours, 1000 ℃ of lower roastings 2 hours namely got catalyst precursor;
(3) catalyst precursor that step (2) is made immerses 16.1mL and contains 17.2mg/mL Pd, the Pd (NO of 1.8mg/mL Pt
3)
2, Pt (NO
3)
2Mixing solutions, under 110 ℃ dry 15 hours, 300 ℃ of lower roastings 3 hours obtained required oxidation state noble metal catalyst;
(4) the catalyzer 10%H that step (3) is made
2-90%N
2Mixed gas and 450 ℃ of lower reductase 12s hour obtain precious metal simple substance attitude catalyzer, and catalyst components is 0.85%Pd/0.09%Pt/10.6%Fe
2O
3/ Al
2O
3
Embodiment 6: catalyzer F:0.59%Pd/ 6.0%NiO/Al
2
O
3
(1) take 4.8g Ni (NO
3)
26H
2O adds deionized water dissolving to 10mL;
(2) with 19.2g Al
2O
3Particle immerses in the aqueous solution of step (1) configuration, and under 110 ℃ dry 24 hours, 1100 ℃ of lower roastings 2 hours namely got catalyst precursor;
(3) catalyst precursor that step (2) is made immerses the PdCl that 10.2mL contains 12mg/mL Pd
2Solution, under 110 ℃ dry 24 hours, 200 ℃ of lower roastings were after 2 hours, washed Cl in catalyzer off with deionized water
-, then under 110 ℃ dry 24 hours, obtain required oxidation state noble metal catalyst;
(4) the catalyzer 10%H that step (3) is made
2-90%N
2Mixed gas and 450 ℃ of lower reductase 12s hour obtain precious metal simple substance attitude catalyzer, and catalyst components is 0.59%Pd/ 6.0%NiO/Al
2O
3
Embodiment 7: catalyzer G:0.48%Pd/0.04%Pt/ 8.5%CrO/Al
2
O
3
(1) take 9.5g Cr (NO
3)
39H
2O adds deionized water dissolving to 10mL;
(2) with 19.2g Al
2O
3Particle immerses in the aqueous solution of step (1) configuration, and under 100 ℃ dry 30 hours, 900 ℃ of lower roastings 2.5 hours namely got catalyst precursor;
(3) catalyst precursor that step (2) is made immerses 10.5mL and contains 9.6mg/mL Pd, the PdCl of 0.9mg/mL Pt
2, PtCl
2Mixing solutions, under 100 ℃ dry 30 hours, 250 ℃ of lower roastings were after 2 hours, washed Cl in catalyzer off with deionized water
-, then under 100 ℃ dry 30 hours, obtain required oxidation state noble metal catalyst;
(4) the catalyzer 10%H that step (3) is made
2-90%N
2Mixed gas and 450 ℃ of lower reductase 12s hour obtain precious metal simple substance attitude catalyzer, and catalyst components is 0.48%Pd/0.04%Pt/ 8.5%CrO/Al
2O
3
Embodiment 8: catalyzer H:0.42%Pd/16.8%NiO/Al
2
O
3
(1) take 4.9g NiCl
26H
2O adds deionized water dissolving to 13mL;
(2) with 24.8g Al
2O
3Particle immerses in the aqueous solution of step (1) configuration, and under 120 ℃ dry 30 hours, 1100 ℃ of lower roastings 2 hours;
(3) repeating step (1)-(2) is 3 times, namely gets catalyst precursor;
(4) catalyst precursor that step (3) is made immerses the PdCl that 14.9mL contains 8.5mg/mL Pd
2Solution, under 120 ℃ dry 30 hours, 200 ℃ of lower roastings were after 2 hours, washed Cl in catalyzer off with deionized water
-, then under 120 ℃ dry 30 hours, obtain required oxidation state noble metal catalyst;
(5) the catalyzer 10%H that step (4) is made
2-90%N
2Under mixed gas and 460 ℃, reduction is 1.5 hours, obtains precious metal simple substance attitude catalyzer, and catalyst components is 0.42%Pd/16.8%NiO/Al
2O
3
Embodiment 9: catalyst I: 0.60%Pd/0.05%Pt/0.04%Rh/ 34.8%CaO/Al
2
O
3
(1) take 30.7g CaCl
2, add deionized water dissolving to 15mL;
(2) with 28.8g Al
2O
3Particle immerses in the aqueous solution of step (1) configuration, and under 110 ℃ dry 10 hours, 1100 ℃ of lower roastings 2 hours namely got catalyst precursor;
(3) catalyst precursor that step (2) is made immerses 22.2mL and contains 12.0mg/mL Pd, 1.0mg/mL Pt, the PdCl of 0.8mg/mL Rh
2,, PtCl
2, RhCl
2Mixing solutions, under 110 ℃ dry 20 hours, 200 ℃ of lower roastings were after 3 hours, washed Cl in catalyzer off with deionized water
-, then under 110 ℃ dry 20 hours, obtain required oxidation state noble metal catalyst;
(4) the catalyzer 10%H that step (3) is made
2-90%N
2Mixed gas and 400 ℃ lower reductase 12 .5 hour obtain precious metal simple substance attitude catalyzer, and catalyst components is 0.60%Pd/0.05%Pt/0.04%Rh/ 34.8%CaO/Al
2O
3
Embodiment 10: catalyzer J:0.57%Pd/26.7%NiO/Al
2
O
3
(1) take 58.1g Ni (NO
3)
26H
2O, 300g Al (NO
3)
39H
2O adds deionized water dissolving to 1000mL;
(2) measure 210mL, 25% NH
3H
2O is diluted to 500mL, then evenly drops under agitation condition in the mixing solutions of step (1) preparation, stirred 80 ℃ of ageings, filtering precipitate 2 hours, afterwards respectively with after under twice, 110 ℃ of 1000mL deionization washing dry 24 hours, 400 ℃ of lower roastings 2 hours;
(3) with below step (2) products therefrom porphyrize to 200 order, moulding, then 900 ℃ of lower roastings 2 hours, be crushed to afterwards the 16-26 order, namely get catalyst precursor;
(4) take the catalyst precursor that 10g step (3) makes, immerse the Pd (NO that 3.5mL contains 16.5mg/mL Pd
3)
2Solution, under 120 ℃ dry 10 hours, 200 ℃ of lower roastings 3 hours obtained required oxidation state noble metal catalyst;
(5) the catalyzer 10%H that step (4) is made
2-90%N
2Mixed gas and 400 ℃ lower reductase 12 .5 hour obtain precious metal simple substance attitude catalyzer, and catalyst components is 0.57%Pd/26.8%NiO/Al
2O
3
Embodiment 11: catalyzer K:0.60%Pd/42.7%NiO/Al
2
O
3
(1) take 47.5g NiCl
26H
2O, 53.3g AlCl
3, add deionized water dissolving to 500mL;
(2) measure 135mL, 25% NH
3H
2O is diluted to 500mL, then evenly drops under agitation condition in the mixing solutions of step (1) preparation, stirred 100 ℃ of ageings, filtering precipitate 2 hours, afterwards respectively with after under twice, 105 ℃ of 1000mL deionization washing dry 20 hours, 500 ℃ of lower roastings 2 hours;
(3) with below step (2) products therefrom porphyrize to 200 order, moulding, then 1100 ℃ of lower roastings 2 hours, be crushed to afterwards the 16-26 order, namely get catalyst precursor;
(4) take the catalyst precursor that 10g step (3) makes, immerse the PdCl that 3.5mL contains 17.1mg/mL Pd
2Solution, under 110 ℃ dry 10 hours, 200 ℃ of lower roastings were after 2 hours, washed Cl in catalyzer off with deionized water
-, then under 110 ℃ dry 24 hours, obtain required oxidation state noble metal catalyst;
(5) the catalyzer 10%H that step (4) is made
2-90%N
2Mixed gas and 450 ℃ of lower reductase 12s hour obtain precious metal simple substance attitude catalyzer, and catalyst components is 0.60%Pd/42.77%NiO/Al
2O
3
Embodiment 12: catalyzer L:0.66%Pd/0.08%Pt/34.6% La
2
O
3
/ Al
2
O
3
(1) take 7.8g La (NO
3)
36H
2O, 68.4g Al (NO
3)
39H
2O adds deionized water dissolving to 500mL;
(2) measure 100mL, 25% NH
3H
2O is diluted to 500mL, then evenly drops under agitation condition in the mixing solutions of step (1) preparation, stirred 100 ℃ of ageings, filtering precipitate 2 hours, afterwards respectively with after under twice, 115 ℃ of 1000mL deionization washing dry 15 hours, 500 ℃ of lower roastings 2 hours;
(3) with below step (2) products therefrom porphyrize to 200 order, moulding, then 1050 ℃ of lower roastings 2 hours, be crushed to afterwards the 16-26 order, namely get catalyst precursor;
(4) take the catalyst precursor that 10g step (3) makes, immerse 3.2mL and contain 20.9mg/mL Pd, the Pd (NO of 2.5mg/mL Pt
3)
2, Pt (NO
3)
2Mixing solutions, under 110 ℃ dry 10 hours, 200 ℃ of lower roastings 2 hours obtained required oxidation state noble metal catalyst;
(5) the catalyzer 10%H that step (4) is made
2-90%N
2Mixed gas and 450 ℃ of lower reductase 12s hour obtain precious metal simple substance attitude catalyzer, and catalyst components is 0.66%Pd/0.08%Pt/34.7% La
2O
3/ Al
2O
3
Embodiment 13: catalyzer M:0.30%Pd/28.1%MgO/Al
2
O
3
(1) take 25.7g Mg (NO
3)
26H
2O, 75g Al (NO
3)
39H
2O adds deionized water dissolving to 1000mL;
(2) take 76g NaHCO
3, be dissolved to 1000mL, then evenly drop under agitation condition in the mixing solutions of step (1) preparation, stirred 100 ℃ of ageings, filtering precipitate 2 hours, afterwards respectively with after under twice, 110 ℃ of 1000mL deionization washing dry 24 hours, 500 ℃ of lower roastings 2 hours;
(3) with below step (2) products therefrom porphyrize to 200 order, moulding, then 1100 ℃ of lower roastings 2 hours, be crushed to afterwards the 16-26 order, namely get catalyst precursor;
(4) take the catalyst precursor that 10g step (3) makes, immerse the PdCl that 1.8mL contains 16.7mg/mLPd
2Solution, under 110 ℃ dry 24 hours, 200 ℃ of lower roastings were after 2 hours, washed Cl in catalyzer off with deionized water
-, then under 110 ℃ dry 24 hours, obtain required oxidation state noble metal catalyst;
(5) the catalyzer 10%H that step (4) is made
2-90%N
2Under mixed gas and 400 ℃, reduction is 3 hours, obtains precious metal simple substance attitude catalyzer, and catalyst components is 0.30%Pd/28.1%MgO/Al
2O
3
Embodiment 14: catalyst n: 0.52%Pd/0.07%Pt/16.4% MgO/Al
2
O
3
(1) take 12.9g Mg (NO
3)
26H
2O, 75g Al (NO
3)
39H
2O adds deionized water dissolving to 500mL;
(2) take 63g NaHCO
3, be dissolved to 1000mL, then evenly drop under agitation condition in the mixing solutions of step (1) preparation, stirred 100 ℃ of ageings, filtering precipitate 2 hours, afterwards respectively with after under twice, 110 ℃ of 1000mL deionization washing dry 24 hours, 500 ℃ of lower roastings 2 hours;
(3) with below step (2) products therefrom porphyrize to 200 order, moulding, then 1100 ℃ of lower roastings 2 hours, be crushed to afterwards the 16-26 order, namely get catalyst precursor;
(4) take the catalyst precursor that 10g step (3) makes, immerse 1.8mL and contain 28.9mg/mL Pd, the Pd (NO of 3.8mg/mL Pt
3)
2, Pt (NO
3)
2Mixing solutions, under 110 ℃ dry 10 hours, 200 ℃ of lower roastings 2 hours obtained required oxidation state noble metal catalyst;
(5) the catalyzer 10%H that step (4) is made
2-90%N
2Mixed gas and 450 ℃ of lower reductase 12s hour obtain precious metal simple substance attitude catalyzer, and catalyst components is 0.52%Pd/0.07%Pt/16.4% MgO/Al
2O
3
Embodiment 15:
Be the above-mentioned catalyzer internal diameter of packing in the silica tube fixed-bed reactor of 8mm, unstripped gas is methane, air, water vapor, and wherein the methane volume fraction is 0.4%, air balance (butt composition); In unstripped gas, the water vapor volume fraction is 4%; The unstripped gas air speed is 80000h
-1(butt air speed), normal pressure, temperature of reaction is 600 ℃.The evaluation result of above-mentioned catalyzer is listed in table 1, and evaluation index is methane conversion.
Embodiment 16:
Catalyzer K carries out the hydrothermal stability experiment, and unstripped gas is methane, air, water vapor, and wherein the methane volume fraction is 0.4%, air balance (butt composition); In unstripped gas, the water vapor volume fraction is 4%; The unstripped gas air speed is 80000h
-1(butt air speed), normal pressure, temperature of reaction is 600 ℃.Evaluation result as shown in Figure 1, evaluation index is methane conversion.
Comparative example 17: catalyzer O:0.67%Pd/Al
2
O
3
(1) with 48g Al
2O
3Particle immerses the PdCl that 25mL contains 12.9mg/mLPd
2Under 110 ℃ of solution dry 24 hours, 200 ℃ of lower roastings were after 2 hours, washed Cl in catalyzer off with deionized water
-, then under 110 ℃ dry 24 hours, obtain required oxidation state noble metal catalyst;
(2) the catalyzer 10%H that step (1) is made
2-90%N
2Mixed gas and 450 ℃ of lower reductase 12s hour obtain precious metal simple substance attitude catalyzer, and the palladium charge capacity is 0.67wt%.
Embodiment 18:
What the present embodiment provided is the catalytic deoxidation reaction experiment result of catalyzer under richness combustion oxygen deprivation condition.The parallel sample H-2 of the catalyzer H in embodiment 8 is adopted in experiment, carries out in internal diameter is the silica tube fixed-bed reactor of 8mm.The feed gas volume fraction set becomes 40%CH
4, 5%O
2, N
2Balance (butt composition); In unstripped gas, the water vapor volume fraction is 4%; The unstripped gas air speed is 80000h
-1(butt air speed), normal pressure, Control for Kiln Temperature is at 350 ℃.The evaluation result of catalyzer is listed in table 1, and evaluation index is oxygen conversion.Above-mentioned experimental result shows that catalyzer of the present invention also can be applicable under the richness combustion oxygen-poor reduction atmosphere of high methane concentration and further expands to the catalyticing combustion process of CO and low-carbon (LC) hydro carbons.
Table 1 catalyst performance table
| The catalyzer title | The transformation efficiency of methane (%) after 1 hour | The transformation efficiency of methane (%) after 500 hours |
| A | 100 | 95 |
| B | 99 | 90 |
| C | 98 | 92 |
| | 100 | 93 |
| E | 95 | 85 |
| | 100 | 96 |
| G | 96 | 85 |
| | 100 | 97 |
| I | 100 | 97 |
| | 100 | 98 |
| K | 100 | 100 |
| L | 98 | 95 |
| M | 100 | 98 |
| | 100 | 99 |
| O | 97 | 75 |
| H-2 | 98 | 95 |
Claims (14)
1. the catalyzer of a low-concentration methane catalyticcombustion, comprise catalytic active component, support of the catalyst Al
2O
3And metal oxide is total to carrier, it is characterized in that: catalytic active component is selected from one or more the combination in platinum family precious metal palladium Pd, platinum Pt, ruthenium Ru, iridium Ir, rhodium Rh, and metal oxide carrier altogether is at least a in magnesium Mg, lanthanum La, iron Fe, manganese Mn, nickel, cobalt Co, chromium Cr, calcium Ca metal oxide.
2. according to the catalyzer of low-concentration methane catalyticcombustion claimed in claim 1, it is characterized in that: described catalytic active component is a kind of in Pd, Pd-Pt, Pd-Rh, Pd-Pt-Rh; In precious metal simple substance, the content of catalytic active component accounts for the 0.01-5% of catalyzer total mass; In simple substance, the content of Pd accounts for the 10-100% of catalytic active component.
3. according to the catalyzer of low-concentration methane catalyticcombustion claimed in claim 1, it is characterized in that: described metal oxide is total to the 5-45% that carrier accounts for the catalyzer total mass.
4. according to the catalyzer of low-concentration methane catalyticcombustion claimed in claim 2, it is characterized in that: in precious metal simple substance, the content of catalytic active component accounts for the 0.1-2% of catalyzer total mass; In simple substance, the content of Pd accounts for the 60-100% of catalytic active component.
5. the preparation method of the described catalyzer of claim 1, it is characterized in that: concrete steps are as follows:
(1) Al
2O
3Carrier and metal oxide are total to any one method in carrier employing pickling process, homogeneous precipitation method, coprecipitation method, thermal decomposition method, are prepared into Binary Mixtures or mixture, and drying and roasting obtain catalyst precursor;
(2) catalytic active component is supported on the catalyst precursor that above-mentioned steps (1) obtains, oxidized catalyst is made in drying and roasting;
(3) oxidized catalyst is reduced, get final catalyzer.
6. according to the preparation method of claim 5 catalyzer, it is characterized in that: described pickling process is dissolved in deionized water for metal oxide is total to the corresponding metallic cation of carrier, with Al
2O
3Carrier immerses this solution, makes mixture, then with the mixture of gained under 100-150 ℃ dry 10-30 hour, 500-1300 ℃ lower roasting 1-4 hour; This step can repeat until obtain needed loading, and get final product.
7. according to the preparation method of claim 5 catalyzer, it is characterized in that: described coprecipitation method is with Al
2O
3Carrier and the metal oxide corresponding metallic cation of carrier altogether are dissolved in deionized water, make the solution of water-soluble salt; Under the condition of vigorous stirring, with finite concentration ammoniacal liquor NH
3H
2O, sodium carbonate Na
2CO
3, sodium bicarbonate NaHCO
3In a kind of slow release type alkaline solution add in the solution of above-mentioned water-soluble salt, with Al
2O
3Carrier and metal oxide be the corresponding metallic cation precipitation of carrier altogether, at 0-150 ℃ of ageing 1-10 hour, obtain containing suspension or the slurry of precipitation, then suspension or slurry are carried out solid-liquid separation, be precipitated solid, moulding, under 100-150 ℃ dry 10-30 hour, 500-1300 ℃ lower roasting 1-4 hour, and get final product.
8. according to the preparation method of claim 5 catalyzer, it is characterized in that: described step (2) is for to adopt equi-volume impregnating to be supported on catalyst precursor catalytic active component, then under 100-150 ℃ dry 10-30 hour, 200-600 ℃ lower roasting 1-4 hour; This step can repeat namely to get oxidized catalyst until obtain needed loading.
9. according to the preparation method of claim 7 catalyzer, it is characterized in that: described Aging Temperature is 40-120 ℃, and digestion time is 5-8 hour.
10. according to the preparation method of claim 9 catalyzer, it is characterized in that: described Aging Temperature is 80-110 ℃.
11. the preparation method according to claim 6 or 7 catalyzer is characterized in that: described maturing temperature is 700-1200 ℃.
12. the preparation method according to claim 8 catalyzer is characterized in that: described maturing temperature is 900-1100 ℃.
13. the preparation method according to claim 12 catalyzer is characterized in that: described maturing temperature is 200-400 ℃.
14. catalyzer claimed in claim 1 is applied to administer or the coal-seam gas catalytic deoxidation is administered methane catalytic combustion process or other hydrocarbon oxidation catalyst subtractive processs as purpose take mine ventilation gas.
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|---|---|---|---|
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|---|---|---|---|
| CN2011103887032A CN103131488A (en) | 2011-11-30 | 2011-11-30 | Low-concentration methane catalytic combustion catalyst and preparation method of the same |
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|---|---|---|---|
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Application publication date: 20130605 |