CN102319574A - Synthesis gas methanation catalyst and preparation thereof - Google Patents
Synthesis gas methanation catalyst and preparation thereof Download PDFInfo
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Abstract
The invention relates to a synthesis gas methanation catalyst, which uses nickel oxide as active ingredients, uses cerium oxide modified medium-pore gamma-aluminum oxide as carriers and use oxide of transition metals of iridium, lanthanum, copper and ferrum or alkaline-earth metals of magnesium and calcium as auxiliary agents, wherein a preparation method of the medium-pore gamma-aluminum oxide adopts a hydrothermal synthesis method, and a nickel base catalyst is prepared by a soaking process, wherein the medium-pore gamma-aluminum oxide has the specific surface area being 200 to 400m<2>/g, the pore volume being 0.2 to 0.9cm<3>/g and the pore diameter being 2 to 15nm, the content of the active ingredients of the nickel oxide is 10 to 30 percent of the total weight of the catalyst, the content of the cerium oxide is 1 to 20 percent of the weight of the aluminum oxide, and the content of the auxiliary agents is 0.1 to 15 percent of the total weight of the catalysts. The synthesis gas methanation catalyst has the advantages that the preparation process is simple, the cerium oxide modified medium-pore gamma-aluminum oxide is used as the catalyst carriers, the obtained nickel base catalyst has good high-temperature resistance and anti-sintering resistance performance and has the advantages of high activity at low temperature, stability at high temperature and high methane selectivity, and the synthesis gas methanation catalyst has an important application value for synthesizing the substitute natural gas and solving the problem of natural gas shortage in the prior art.
Description
Technical field
A kind of synthesis gas methanation catalyst of the present invention and preparation thereof belong to Preparation of catalysts and application thereof, in particular to a kind of be carrier with the mesopore gama-alumina, can be used for the catalyst of the direct synthesizing methane of coal based synthetic gas.
Background technology
Efficient and green utilization of fossil resource is long-term research content.Natural gas is as a kind of cleaning, the efficient and green gas energy, and its calorific value is high, it is little to pollute, and still, the China's natural gas reserves are abundant.The coal system of utilization substitute natural gas (Substitute Natural Gas-SNG); Can make full use of the synthetic energy starved natural gas of low-grade coal resources such as brown coal of China's abundant efficiently, cleanly; Satisfy domestic demand [energy .2010 of China and foreign countries, 15 (6): 28 to natural gas; Chemical fertilizer design 2010,48 (2): 19].It is thus clear that, according to the characteristics of the rich coal weak breath of China, to utilize and enrich coal resources relatively, develop actively coal preparing natural gas (SNG) technology is the developing direction of following low-grade coal comprehensive utilization of resources, for realizing that low-carbon economy and energy-saving and emission-reduction have important practical significance.
The key of coal preparing natural gas technology is the methanation synthetic technology, and wherein, core technology is a methanation catalyst.Methanation reaction is the strong exothermal reaction under catalyst action, necessarily requires methanation catalyst to keep stable performance at high temperature, and has higher activity at low temperatures.At present, methanation catalyst adopts nickel as main active component mostly, and the carrier that generally uses is Al
2O
3It is mainly from the [energy .2010 of China and foreign countries of Britain Dai Wei company, German LURGI and rope company of Denmark Top; 15 (6): 28]; The catalyst system of nickel-alumina just that wherein representative methanation catalyst patent US3988262 and US398826 use; Still there is high temperature active component easy-sintering in situation from existing catalyst operation and the inactivation problem.
CN101380581A discloses a kind of novel methanation catalyst and preparation method thereof, and catalyst each component mass percent consists of: Al
2O
3: 70-86%; NiO:12-20%; La
2O
3: 0.5-5%; MgO:0.5-5%; CeO
2: 0.1-5%; CaO:0.1-3%; Na
2O:0.1-1%; BaO:0.01-2%; Catalyst specific surface is 100-180m
2/ g; Reaction temperature is 300 ℃, reaction pressure 1MPa, carbon monoxide conversion ratio 100%, methane selectively 99.9-100%.CN102029162A discloses a kind of wide temperature range type full methanation Catalysts and its preparation method; Active component is nickel (10-75%); Carrier is one or more and a zirconic composition (zirconium al atomic ratio 0.01-1.45) of aluminium oxide and nickel aluminide; Auxiliary agent be lanthana or with the composition (0.1-15%) of nickel lanthanum compound, be suitable for temperature 280-650 ℃, pressure 2-4MPa.CN101890353A discloses a kind of high-temperature methanation catalyst, and catalyst consists of: active component is NiO (15-70%); Metal oxide Al
2O
3And ZrO
2Be carrier (Al
2O
3: 25-75%, ZrO
2: 10-25%); Metal oxide Re
2O
3And at least a in the magnesium, copper, chromium metal oxide is auxiliary agent (Re
2O
3: 2-7%, the methanation reaction temperature is 700 ℃, carbon monoxide conversion ratio 85-99%, methane selectively 76.3-95.8%.CN101786003A discloses a kind of Catalysts and its preparation method that is used for preparing natural gas by methanation, and the catalyst composition is: Ni content is 20-50%, and ree content is 1-8%, and Sr, V, Ca, Cr are 0.5-5%, and all the other are Al
2O
3Reaction temperature is 280-700 ℃, pressure 2-6MPa, carbon monoxide conversion ratio 74.6-99%, methane selectively 76.9-94.1%.CN101844080A discloses a kind of Catalysts and its preparation method that is used for preparing methane by synthetic gas, and the mass percent of each component of catalyst is respectively: Al
2O
3: 75-85%; NiO:15-25%; MgO:1-5%; La
2O
3: 0.5-3%; Na
2O:0.2～1%, reaction temperature are 450-500 ℃, and pressure 2.5MPa, carbon monoxide conversion ratio be greater than 94%, and methane selectively is greater than 88%, and when temperature is lower than 300 ℃ or be higher than 700 ℃, the carbon monoxide conversion ratio reduces greatly.CN 101716513A disclosed a kind of be the methanation catalyst and the application of carrier with the rare earth cerium oxide, the catalyst activity component is NiO (10-75%), carrier is CeO
2Base rare-earth oxide (10-90%), auxiliary agent is La
2O
3(0.1-15%).Three sections range of reaction temperature of methanation are between 250-750 ℃, and the carbon monoxide conversion ratio is 85-90%.CN101537357A discloses a kind of methanation catalyst prepared by synthetic gas, and catalyst consists of: iron oxide 1-20%, cobalt oxide 1-30%; Nickel oxide 1-30%, rare earth oxide 0-10%, molybdenum oxide 0-10%; Carrier is a carborundum; Its content 50-97%, the methanation reaction temperature is between 200-400 ℃, and methane selectively is greater than 80%.CN102020525A discloses a kind of Ni/SiC catalyst and has transformed the application in the system methane at synthesis gas; Active component nickel content is 1-20% in the catalyst; Carrier is the carborundum with thermal conductive resin and mechanical strength, and the methanation reaction temperature is 300-800 ℃, and pressure is 0.1-10MPa; The carbon monoxide conversion ratio is greater than 90%, and methane selectively is greater than 85%.
The carrier of methanation catalyst is selected inorganic material such as aluminium oxide or cerium oxide usually for use, but these material heat-transfer effects are poor, and in the methanation reaction of strong heat release, heat can not scatter and disappear fast, catalyst hot-spot and cause the active component sintering.
Summary of the invention
A kind of synthesis gas methanation catalyst of the present invention and preparation thereof; It is poor because of heat-transfer effect that purpose is to solve in the synthesis gas methanation catalyst; The problem of active component easy-sintering at high temperature, thus the methanation catalyst of a kind of low temperature high activity and the anti-sintering of high temperature is provided.
A kind of synthesis gas methanation catalyst of the present invention; It is characterized in that this catalyst comprises active component, carrier and auxiliary agent; Wherein, Nickel oxide is an active component, and the mesopore gama-alumina of cerium oxide modification is a carrier, and the oxide of transition metal iridium, lanthanum, copper, iron or alkaline-earth metal magnesium, calcium is an auxiliary agent.
Above-mentioned a kind of synthesis gas methanation catalyst, the content that it is characterized in that described active component nickel oxide is the 10-30% of total catalyst weight.
Above-mentioned a kind of synthesis gas methanation catalyst, the specific area that it is characterized in that described mesopore gama-alumina is 200-400m
2/ g, pore volume are 0.2-0.9cm
3/ g, the aperture is 2-15nm.
Above-mentioned a kind of synthesis gas methanation catalyst, the content that it is characterized in that described cerium oxide is the 1-20% of mesoporous aluminas weight.
Above-mentioned a kind of synthesis gas methanation catalyst is characterized in that described auxiliary agent content is the 0.1-15% of total catalyst weight.
Above-mentioned a kind of synthesis gas methanation catalyst is characterized in that described auxiliary agent is one or more in transition metal iridium, lanthanum, copper, iron, alkaline-earth metal magnesium and the calcium oxide.
The preparation of above-mentioned a kind of synthesis gas methanation catalyst is characterized in that this preparation follows these steps to carry out:
I, at first with the polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer, is called for short P123; The mol ratio of aluminium is that 100-140 is dissolved in the ethanol in its weight and the aluminium salt, after treating fully to dissolve, and one or both in adding aluminium isopropoxide, aluminium chloride or the aluminum nitrate; Stir 4-8h down at 20-40 ℃; Place 60-80 ℃ drying box constant temperature 48h, at 400-600 ℃ of roasting 4-6h, promptly obtain the mesopore gama-alumina then;
II, secondly immerses the prepared mesopore gama-alumina of I in the cerous nitrate solution, through dipping, at 100-120 ℃ of dry 2-3h down, obtains the mesopore gamma-aluminium oxide carrier of cerium oxide modification at 400-500 ℃ of following calcination process 2-3h;
III, then the mesopore gama-alumina of the prepared cerium oxide modification of II is immersed in the nickel nitrate solution,,, obtain supported nickel catalyst at 400-500 ℃ of following calcination process 2-3h at 100-120 ℃ of dry 2-3h down through dipping;
IV, last; The resulting supported nickel catalyst immersion of III is contained in the nitrate solution of one or more transition metal iridium, lanthanum, copper, iron or alkaline-earth metal magnesium or calcium; Again through dipping; At 100-120 ℃ of following dry 2-3h, obtain the loading type nickel-based catalyst of different additive modifications at 400-500 ℃ of following roasting 2-3h.
Above-mentioned a kind of synthesis gas methanation catalyst is characterized in that can be used for the process that synthesis gas is converted into methane, also can be used for the methanation of carbon dioxide.
A kind of synthesis gas methanation catalyst of the present invention and preparation thereof; Its advantage is; Have the carrier of the gama-alumina of central hole structure owing to adopt as nickel-base catalyst; Its flourishing mesopore hole helps the transmission of reaction heat in the methanation reaction, thereby avoids the excess temperature sintering of active component, and corresponding high-activity stable property.Be suitable for the directly synthetic instead of natural gas of coal based synthetic gas.
Catalyst of the present invention is used for the synthesis gas methanation reaction, and the catalytic performance test is carried out in the high pressure micro-reaction device, and reaction temperature is 190-650 ℃, and reaction pressure is 1-6MPa, H in the synthesis gas
2/ CO ratio is 3-3.5.
Description of drawings
Fig. 1 is the X-ray diffractogram of mesopore gama-alumina of the present invention.
The specific embodiment
Technical scheme of the present invention can be passed through specific embodiment further explain; Said those skilled in the art are after having read this specific embodiment; Can understand and embodiment of the present invention, its said beneficial effect also can obtain through concrete embodiment embodying.
The specific embodiment 1
Take by weighing 1g P123 and be dissolved in ethanol, after treating fully to dissolve, add the 2g aluminium isopropoxide, 40 ℃ are stirred 4h, place 60 drying box freeze-day with constant temperature 48h, through 400 ℃ of roasting 4h, obtain mesoporous aluminas, and specific area is 329.5m
2/ g, pore volume 0.485cm3/g, aperture 4.9nm.Take by weighing 2.48 the gram nickel nitrates and 0.95 the gram cerous nitrate be configured to solution respectively; 2.5 gram mesoporous aluminas carriers are immersed earlier in the solution of cerous nitrate, dry 3h under 100 ℃, and behind 450 ℃ of roasting 2h; Again it is immersed in the nickel nitrate solution; Sample behind the dipping is dry 2h under 120 ℃, and 450 ℃ of roasting 4h obtain supported nickel catalyst; Then it is immersed in the solution by 0.6 gram nitric acid iridium configuration, the sample behind the dipping is dry 2h under 120 ℃, and 500 ℃ of roasting 4h obtain the catalyst of modification, with its compression molding, obtain 40-60 purpose catalyst granules.Be used for the synthesis gas methanation reaction, 200 ℃ of temperature, pressure 1.5MPa, air speed is 9000h
-1, H in the synthesis gas
2/ CO ratio is 3.In the reaction time of 200h, the carbon monoxide conversion ratio is 90%, and methane selectively is 100%.
The specific embodiment 2
According to same procedure in the specific embodiment 1, synthetic mesoporous aluminas supported nickel catalyst.Then it is immersed in the solution by 0.4 gram magnesium nitrate configuration, the sample behind the dipping is dry 3h under 120 ℃, and 500 ℃ of roasting 3h obtain the catalyst of modification, with its compression molding, obtain 40-60 purpose catalyst granules.Be used for the synthesis gas methanation reaction, 400 ℃ of temperature, pressure 1.5MPa, air speed is 9000h
-1, H in the synthesis gas
2/ CO ratio is 3.In the reaction time of 200h, the carbon monoxide conversion ratio is 90%, and methane selectively is 100%.
The specific embodiment 3
Take by weighing 1g P123 and be dissolved in ethanol, after treating fully to dissolve, add the 2.5g aluminium isopropoxide, 40 ℃ are stirred 4h, place 60 drying box freeze-day with constant temperature 48h, through 400 ℃ of roasting 4h, obtain mesoporous aluminas, and specific area is 254.2m
2/ g, pore volume 0.405cm3/g, aperture 3.42nm.。Take by weighing 2.48 gram nickel nitrates and 0.95 gram cerous nitrate is configured to solution respectively, 2.5 gram mesoporous aluminas carriers immersed earlier in the solution of cerous nitrates, to be impregnated after; Sample is dry 2h under 120 ℃; After 450 ℃ of roastings, again it is immersed in the nickel nitrate solution, the sample behind the dipping is dry 2h under 120 ℃; 450 ℃ of roasting 4h obtain supported nickel catalyst; Then it is immersed in the solution by 0.6 gram nitric acid iridium configuration, the sample behind the dipping is dry 3h under 100 ℃, and 500 ℃ of roasting 4h obtain the catalyst of modification, with its compression molding, obtain 40-60 purpose catalyst granules.Be used for the synthesis gas methanation reaction, 240 ℃ of temperature, pressure 1.5MPa, air speed is 9000h
-1, H in the synthesis gas
2/ CO ratio is 3.In the reaction time of 200h, the carbon monoxide conversion ratio is 92%, and methane selectively is 100%.
The specific embodiment 4
Take by weighing 1g P123 and be dissolved in ethanol, after treating fully to dissolve, add the 3g aluminium isopropoxide, 40 ℃ are stirred 4h, place 60 ℃ drying box freeze-day with constant temperature 48h, through 400 ℃ of roasting 4h, obtain mesoporous aluminas, and specific area is 239.8m
2/ g, pore volume 0.254cm
3/ g, aperture 3.4nm.。Take by weighing 2.48 gram nickel nitrates and 0.95 gram cerous nitrate is configured to solution respectively, 2.5 gram mesoporous aluminas carriers are immersed earlier in the solution of cerous nitrates, the sample behind the dipping is at 120 ℃ of dry 2h down; After 450 ℃ of roastings; Again it is immersed in the nickel nitrate solution, behind the dipping, dry 2h under 120 ℃; 450 ℃ of roasting 4h obtain supported nickel catalyst.Then it is immersed in the solution by 0.4 gram magnesium nitrate configuration, behind the dipping, dry 2h under 120 ℃, 500 ℃ of roasting 4h obtain the catalyst of modification, with its compression molding, obtain 40-60 purpose catalyst granules.Be used for the synthesis gas methanation reaction, 280 ℃ of temperature, pressure 1.5MPa, air speed is 9000h
-1, H in the synthesis gas
2/ CO ratio is 3.In the reaction time of 200h, the carbon monoxide conversion ratio is 96%, and methane selectively is 100%
The specific embodiment 5
Take by weighing 2g P123 and be dissolved in ethanol, after treating fully to dissolve, add the 3g aluminium isopropoxide, 40 ℃ are stirred 4h, place 60 drying box freeze-day with constant temperature 48h, through 400 ℃ of roasting 4h, obtain mesoporous aluminas, and specific area is 256.7m
2/ g, pore volume 0.82cm3/g, aperture 7.90nm.Take by weighing 2.48 gram nickel nitrates and 0.95 gram cerous nitrate is configured to solution respectively, 2.5 gram mesoporous aluminas carriers immersed earlier in the solution of cerous nitrates, to be impregnated after; Sample is dry 2h under 120 ℃; After 450 ℃ of roastings, again it is immersed in the nickel nitrate solution, the sample behind the dipping is dry 2h under 100 ℃; At 450 ℃ of roasting 4h, obtain supported nickel catalyst; With in the solution of its immersion by 0.6 gram nitric acid iridium configuration, flood back dry 2h under 120 ℃ then, 500 ℃ of roasting 4h obtain the catalyst of modification, with its compression molding, obtain 40-60 purpose catalyst granules.Be used for the synthesis gas methanation reaction, 450 ℃ of temperature, pressure 1.5MPa, air speed is 9000h
-1, H in the synthesis gas
2/ CO ratio is 3.In the reaction time of 200h, the carbon monoxide conversion ratio is 86%, and methane selectively is 100%.
The specific embodiment 6
According to same procedure in the specific embodiment 5, synthetic mesoporous aluminas supported nickel catalyst.Then it is immersed in the solution by 0.4 gram magnesium nitrate configuration, the sample behind the dipping is dry 2h under 120 ℃, and 500 ℃ of roasting 4h obtain the catalyst of modification, with its compression molding, obtain 40-60 purpose catalyst granules.Be used for the synthesis gas methanation reaction, 600 ℃ of temperature, pressure 1.5MPa, air speed is 9000h
-1, H in the synthesis gas
2/ CO ratio is 3.In the reaction time of 200h, the carbon monoxide conversion ratio is 65%, and methane selectively is 100%.
Claims (8)
1. synthesis gas methanation catalyst; It is characterized in that this catalyst comprises active component, carrier and auxiliary agent, wherein, nickel oxide is an active component; The mesopore gama-alumina of cerium oxide modification is a carrier, and the oxide of transition metal iridium, lanthanum, copper, iron or alkaline-earth metal magnesium, calcium is an auxiliary agent.
2. according to the described catalyst of claim 1, the content that it is characterized in that described active component nickel oxide is the 10-30% of total catalyst weight.
3. according to the described catalyst of claim 1, the specific area that it is characterized in that described mesopore gama-alumina is 200-400m
2/ g, pore volume are 0.2-0.9cm
3/ g, the aperture is 2-15nm.
4. according to the described catalyst of claim 1, the content that it is characterized in that described cerium oxide is the 1-20% of mesoporous aluminas weight.
5. according to the described catalyst of claim 1, it is characterized in that described auxiliary agent content is the 0.1-15% of total catalyst weight.
6. according to the described catalyst of claim 1, it is characterized in that described auxiliary agent is one or more in transition metal iridium, lanthanum, copper, iron, alkaline-earth metal magnesium and the calcium oxide.
7. the described Preparation of catalysts of claim 1 is characterized in that this preparation follows these steps to carry out:
I, at first, with the polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer, the mol ratio of aluminium is that 100-140 is dissolved in the ethanol in its weight and the aluminium salt; After treating fully dissolving; In adding aluminium isopropoxide, aluminium chloride or the aluminum nitrate one or both stir 4-8h down at 20-40 ℃, place 60-80 ℃ drying box constant temperature 48h; At 400-600 ℃ of roasting 4-6h, promptly obtain the mesopore gama-alumina then;
II, secondly immerses the prepared mesopore gama-alumina of I in the cerous nitrate solution, through dipping, at 100-120 ℃ of dry 2-3h down, obtains the mesopore gamma-aluminium oxide carrier of cerium oxide modification at 400-500 ℃ of following calcination process 2-3h;
III, then the mesopore gama-alumina of the prepared cerium oxide modification of II is immersed in the nickel nitrate solution,,, obtain supported nickel catalyst at 400-500 ℃ of following calcination process 2-3h at 100-120 ℃ of dry 2-3h down through dipping;
IV, last; The resulting supported nickel catalyst immersion of III is contained in the nitrate solution of one or more transition metal iridium, lanthanum, copper, iron or alkaline-earth metal magnesium or calcium; Again through dipping; At 100-120 ℃ of following dry 2-3h, obtain the loading type nickel-based catalyst of different additive modifications at 400-500 ℃ of following roasting 2-3h.
8. the described catalyst of claim 1 is characterized in that can be used for the process that synthesis gas is converted into methane, also can be used for the methanation of carbon dioxide.
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| CN102600860A (en) * | 2012-02-15 | 2012-07-25 | 华东理工大学 | Catalyst suitable for complete methanation of middle-low-temperature synthetic gas and preparation method thereof |
| CN102626628A (en) * | 2012-05-17 | 2012-08-08 | 太原理工大学 | Preparation method of synthetic gas methanation catalyst |
| CN103203237A (en) * | 2013-05-02 | 2013-07-17 | 神华集团有限责任公司 | Aluminum oxide loaded methanation catalyst |
| CN104209127A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Ferronickel bimetallic methanation catalyst and preparation and application thereof |
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