CN104399482A - Iron-containing natural ore loaded nickel catalyst for methanation and preparation method thereof - Google Patents
Iron-containing natural ore loaded nickel catalyst for methanation and preparation method thereof Download PDFInfo
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- CN104399482A CN104399482A CN201410637744.4A CN201410637744A CN104399482A CN 104399482 A CN104399482 A CN 104399482A CN 201410637744 A CN201410637744 A CN 201410637744A CN 104399482 A CN104399482 A CN 104399482A
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Abstract
The invention discloses an iron-containing natural ore loaded nickel catalyst for methanation and a preparation method thereof. Nickel oxide accounts for 2-15 wt% of the catalyst. Based on redox capacity of a carrier and its occurring interaction between iron and loaded nickel and by measures of adjusting nickel loading capacity, calcination temperature of the carrier, calcination temperature of the catalyst, reduction temperature of the catalyst and the like, a loaded ferro-nickel bimetallic methanation catalyst is prepared. The catalyst prepared in the invention has characteristics of low nickel loading capacity, high activity, good stability, high strength and the like. The preparation process is simple. Raw materials are low-cost and easily available. The catalyst is economic and environmentally-friendly. The catalyst is suitable for CO2/CO methanation process of coke-oven gas, coal-based and biomass-based synthesis gas and the like under various H/C conditions. Due to characteristics of the catalyst such as low nickel loading capacity, high abrasive resistance and the like, the catalyst is especially suitable for methanation operation in a fluidized bed, a slurry reactor or a moving bed.
Description
Technical field
The present invention relates to catalyst and preparing technical field thereof, particularly relate to the iron content natural crystal nickel-loaded catalyst and preparation method thereof for methanation.
Background technology
The current resources situation of " rich coal, oil-poor, weak breath ", determine by coal synthetic natural gas, national consumption market is delivered to from remote rich coal district again through long-distance transport pipes, as traditional Coal Transport and the means of conversion important supplement, in energy security, energy-saving and emission-reduction, coal high-efficiency utilization etc., there is its own strategic significance, meanwhile, be also the effective means solving the haze weather that current a large amount of directly fire coal causes.
Methanation catalyst is as one of large core technology of coal synthetic natural gas (SNG) two (methanation catalyst and catalytic reactor exploitation), and its developmental research is long-standing.Methanation technology comparatively ripe at present mainly comprises Britain Dai Wei, Top of Denmark rope and German Nuqi Technology.The active component of major part catalyst is the 8th race's metal, and wherein most study is nickel, and the carrier selected comprises aluminium oxide, silica, magnesia etc., meanwhile, adds multiple alkali and alkaline earth metal ions oxide and regulates and controls its active and stability as auxiliary agent.The deficiency of main existence comprises: nickel is as active component separately, limited activity, and for improving disposal ability and conversion ratio, business-like methanation catalyst generally adopts high year nickel amount catalyst; For improving activity and the stability of catalyst, the carrier of a large amount of promoter and multiple programs complexity and catalyst preparation technology are used, and cause catalyst raw material and preparation cost to increase.Chinese patent CN102513124A discloses a kind of gas employing methanation of coke oven catalyst, active component is nickel, carrier is aluminium oxide or titanium dioxide, there is features such as using air speed is high, activity is high, serviceability temperature wide ranges, but the carrying capacity 25-50% of its active component nickel oxide, and use the rare earth element of 0.5-10% as the first auxiliary agent, use Mn, V and Ce etc. of 2-20% as the second auxiliary agent, consumption of raw materials amount is large, and cost increases.Chinese patent CN101716513A discloses a kind of loaded catalyst of coal gas completely methanated by synthesis gas, CO/CO
2methanation activity is high, and be suitable for synthesis gas multistage methanation production synthetic natural gas, its active component nickel oxide content is 10-75% (preferred 20-60%), and carrier is cerium oxide base rare-earth oxide.Chinese patent CN103752315A discloses a kind of Metal Phase carrier (metallic nickel, metallic copper, metallic iron or metal copper-nickel alloy) support type methanation catalyst, its Metal Phase carrier is diameter is 4-150 μm, length is the fiber of 2-10mm or the monolithic substrate by this fiber sintering, for obtaining the Metal Phase carrier of top layer porous, use aluminium powder dipping and Alloying Treatment, carry out subsequently taking out aluminium process, described carrier thermal conductivity is good, permeability is high, but preparation process is quite complicated, production cost is high.
Summary of the invention
For the deficiency of conventional methanation catalyst, the invention provides with iron content natural crystal is the methanation catalyst and preparation method thereof of carrier loaded nickel, implements technical scheme of the present invention as follows:
For the iron content natural crystal supported nickel catalyst of methanation, the carrier of this catalyst is the precalcining thing of iron content natural crystal particle, in this catalyst, the content of the nickel of institute's load is with nickel oxide mass percent for 2-15%, and in catalyst, the atomic ratio of nickel and iron is between 0.03:1 to 20:1.
Described catalyst consists of 20%H through gas volume
2and 80%N
2, air speed is 10000h
-1reducing gases at 500 DEG C after reductase 12 h, in catalyst, the atomic ratio of metal state nickel and metallic state iron is between 1:1 to 5:1.
Described iron content natural crystal is olivine, magnetic iron ore, bloodstone, limonite, siderite, nickel sulfide ore or lateritic nickel ore, or their two or more mixture.
For the preparation method of the iron content natural crystal supported nickel catalyst of methanation, comprise the steps:
(1) described iron content natural crystal is ground into graininess, granularity is 0.05-8.0mm, then at 500-1300 DEG C, calcines 1-5h, is cooled to room temperature, obtain pelleted substrate;
(2) be the nickel salt aqueous solution of 0.1-8.0mol/L by described recipe configuration cation concn, adopt infusion process, the carrier that configured nickel salt aqueous solution and step (1) obtain is mixed, dipping absorption, drying, roasting, obtains required loaded catalyst.
Preferably, the calcining heat of iron content natural crystal particle described in step (1) is between 600-1100 DEG C.
Preferably, the infusion process described in step (2) is equi-volume impregnating.
The preparation method of described catalyst, in step (2), described nickel salt is the combination of in nickel nitrate, nickelous sulfate, nickel chloride, nickel acetate a kind or at least 2 kinds, preferred nickel nitrate.
The preparation method of described catalyst, in step (2), described dipping adsorption temp is no more than 100 DEG C, preferred 10-40 DEG C; Dipping adsorption time is 4-24h, preferred 6-12h.
The preparation method of described catalyst, in step (2), described baking temperature is 100-150 DEG C, preferred 100-120 DEG C; Drying time is 1-6h, preferred 2-4h.
The preparation method of described catalyst, in step (2), described sintering temperature is 300-600 DEG C, preferred 350-500 DEG C; Roasting time is 1-10h, preferred 2-5h.
Iron content natural crystal supported nickel catalyst of the present invention, because nickel-loaded and carrier compose the alternate interaction of iron deposit, can obtain loading type iron nickel alloy catalyst, active in carrying iron or nickel-loaded catalyst separately; Because carrier is the iron-bearing mineral of natural dispersive, through calcining, can form the active phase of reducibility iron oxide of below particle diameter 50nm on its surface, induction nickel-loaded is uniformly distributed by this activity, finally forms nano level metal active sites; Part is reducible at reaction conditions for selected ore carrier, based on the carrier of partial reduction oxygen carrying capability and and active sites between interaction, improve the active and stability of methanation catalyst active metal catalyst.
The preparation method of the methanation catalyst of iron content natural crystal nickel-loaded of the present invention, the migration of element that carrier calcining causes its phase transformation alternate with body with surface, affects the quantity of reducibility ferro element, dispersiveness and existence form; Catalyst sintering temperature affects the dispersiveness of active metal and the interaction with carrier thereof; Catalyst reduction temperature affects catalyst reduction degree, i.e. the quantity of iron atom in dilval, and the oxidation-reduction quality of carrier; Thus, the effective means that nickel amount, carrier calcining heat, catalyst sintering temperature and catalyst reduction temperature become optimization of catalysts activity is carried.Simultaneously because natural crystal carrier is before use through high-temperature calcination, therefore its heat endurance and chemical stability high, improve the anti-caking power of this catalyst.
The invention has the beneficial effects as follows:
Prepare the methanation catalyst of a kind of low year nickel amount, high activity, high stability and high strength, its preparation process is simple, economic environmental protection, is applicable to CO under the multiple H/C conditions such as oven gas, coal-based and Biomass Syngas
2the methanation of/CO, is especially applicable to fluid bed, slurry bed system and moving bed methanation operation.
Accompanying drawing explanation
Accompanying drawing is iron content natural crystal particulate load Raney nickel preparation flow figure.
Detailed description of the invention
Further describe for iron content natural crystal supported nickel catalyst of methanation and preparation method thereof disclosed in this patent below by specific embodiment, but the present invention is not by the restriction of following embodiment.
Embodiment 1
It is 0.38-0.83mm that raw ore olivine (originating from Hubei) is crushed to particle diameter, 4.5h is calcined at 1000 DEG C, taking 6g Nickelous nitrate hexahydrate is dissolved in 2.2ml deionized water, then this nickel nitrate solution is added 20g in the olivine particles of precalcining, abundant stirring, steeped overnight, after 105 DEG C of dry 1h, 3 DEG C/min rises to 350 DEG C, roasting 4.5h, obtain 7wt%NiO-olivine methanation catalyst, its rate of wear is 10% (method of testing is with reference to professional standard HG/T 2976-2011); Loaded in fixed bed reactors by above-mentioned for 1g catalyst, temperature 500 DEG C, gas volume consists of 20%H
2and 80%N
2, air speed 10000h
-1reductase 12 h under condition.Reduction rear catalyst is used for fixed bed methanation reaction, concrete reaction condition and the results are shown in subordinate list 1.
Embodiment 2
It is 0.38-0.83mm that nickel ores (originating from Jilin) is crushed to particle diameter, 4.5h is calcined at 900 DEG C, 6g Nickelous nitrate hexahydrate is dissolved in 2.2ml deionized water, then this nickel nitrate solution is added 20g in the nickel ores particle of precalcining, abundant stirring, steeped overnight, after 105 DEG C of dry 1h, 3 DEG C/min rises to 500 DEG C, roasting 4.5h, obtain 7wt%NiO-nickel ore methanation catalyst, its rate of wear is 10% (method of testing is with reference to professional standard HG/T 2976-2011); Above-mentioned for 1g catalyst is loaded in fixed bed reactors, is directly used in methanation reaction without reduction, concrete reaction condition and the results are shown in subordinate list 1.
Comparative example 1
Certain commercial catalysts being crushed to particle diameter is 0.38-0.83mm, this catalyst of 1g is loaded in fixed bed reactors, according to this catalyst operation instruction, at 400 DEG C, reduces 4h, catalyst after reduction is used for fixed bed methanation reaction, concrete reaction condition and the results are shown in subordinate list 1.
Table 1: the evaluation result of the fixed bed methanation reaction of catalyst prepared by each embodiment and certain commercial catalysts.
| Embodiment | H 2/CO 2 | Reduction temperature/DEG C | Reaction temperature/DEG C | Air speed/h -1 | CO 2Conversion ratio | CH 4Selective |
| 1 | 6 | 500 | 400 | 11000 | 98.4 | 99.9 |
| 1 | 3.2 | 500 | 350 | 11000 | 60.4 | 98.4 |
| 1 | 3.2 | 500 | 400 | 11000 | 67.2 | 98.7 |
| 1 | 3.2 | 500 | 450 | 11000 | 62.9 | 96.7 |
| 1 | 3.2 | 500 | 500 | 11000 | 59.3 | 91.1 |
| 2 | 4 | Do not reduce | 400 | 11000 | 72.8 | 92.4 |
| Comparative example 1 | 6 | 400 | 400 | 11000 | 98.2 | 99.9 |
| Comparative example 1 | 3.2 | 400 | 400 | 11000 | 67.1 | 98.8 |
Result shows, catalyst of the present invention activity within the scope of 350-500 DEG C is higher, the methanation reaction under multiple H/C condition can be adapted to, under the operating condition that business methanation catalyst is recommended, active close with it, and in embodiment 1 and comparative example 1, the temperature programmed oxidation reaction result of the reacted catalyst of 5h shows, catalyzer coke content (2.7%) prepared by the present invention is much smaller than commercial catalysts (12.8%), and catalyst stability is excellent; But catalyst oxidation nickel content prepared by the present invention is only 7%, far below year nickel amount of commercial catalysts more than 40%, and carrier of the present invention is for only to need the simply dealt reserves natural minerals that enriches, without the need to various auxiliary agent, simplify preparation flow, reduce cost of material and preparation cost; Owing to adopting the very high natural crystal particle of intensity as carrier and lower active component carrying capacity, this catalyst wearability is better, is especially applicable to fluid bed, slurry bed system and moving bed methanation operation.
Table 2: the XRF composition analysis (wt%) of nickel minerals (Jilin).
| MgO | SiO 2 | Fe 2O 3 | Al 2O 3 | SO 3 | CaO | NiO | K 2O | Na 2O | CuO | TiO 2 | P 2O 5 |
| 10.50 | 45.10 | 19.60 | 8.73 | 4.90 | 4.85 | 1.72 | 1.53 | 1.54 | 0.81 | 0.59 | 0.16 |
Table 3: the XRF composition analysis (wt%) of olivine (Hubei).
| MgO | SiO 2 | Fe 2O 3 | Al 2O 3 | Cr 2O 3 | CaO | NiO |
| 51.80 | 36.50 | 9.14 | 0.88 | 0.60 | 0.37 | 0.36 |
Claims (9)
1. the iron content natural crystal supported nickel catalyst for methanation, it is characterized in that, the carrier of this catalyst is the precalcining thing of iron content natural crystal particle, in this catalyst, the content of the nickel of institute's load counts 2-15% with nickel oxide mass percent, and in catalyst, the atomic ratio of nickel and iron is between 0.03:1 to 20:1.
2. catalyst as claimed in claim 1, it is characterized in that, described catalyst consists of 20%H through gas volume
2and 80%N
2, air speed is 10000h
-1reducing gases at 500 DEG C after reductase 12 h, in catalyst, the atomic ratio of metal state nickel and metallic state iron is between 1:1 to 5:1.
3. catalyst as claimed in claim 1 or 2, it is characterized in that, described iron content natural crystal is olivine, magnetic iron ore, bloodstone, limonite, siderite, nickel sulfide ore or lateritic nickel ore, or their two or more mixture.
4. the preparation method of catalyst as claimed in claim 1 or 2, is characterized in that comprising the steps:
(1) described iron content natural crystal is ground into graininess, granularity is 0.05-8.0mm, then at 500-1300 DEG C, calcines 1-5h, is cooled to room temperature, obtain pelleted substrate;
(2) be the nickel salt aqueous solution of 0.1-8mol/L by described recipe configuration cation concn, adopt infusion process, the carrier that configured nickel salt aqueous solution and step (1) obtain is mixed, dipping absorption, drying, roasting, obtains required loaded catalyst.
5. the preparation method of catalyst as claimed in claim 3, is characterized in that comprising the steps:
(1) described iron content natural crystal is ground into graininess, granularity is 0.05-8.0mm, then at 500-1300 DEG C, calcines 1-5h, is cooled to room temperature, obtain pelleted substrate;
(2) be the nickel salt aqueous solution of 0.1-8mol/L by described recipe configuration cation concn, adopt infusion process, the carrier that configured nickel salt aqueous solution and step (1) obtain is mixed, dipping absorption, drying, roasting, obtains required loaded catalyst.
6. the preparation method of catalyst as claimed in claim 4, it is characterized in that, in step (1), the calcining heat of described iron content natural crystal particle is between 600-1100 DEG C.
7. the preparation method of catalyst as claimed in claim 5, it is characterized in that, in step (1), the calcining heat of described iron content natural crystal particle is between 600-1100 DEG C.
8. the preparation method of catalyst as claimed in claim 4
In step (2), described nickel salt is the combination of in nickel nitrate, nickelous sulfate, nickel chloride, nickel acetate a kind or at least 2 kinds;
In step (2), described infusion process is equi-volume impregnating;
In step (2), described dipping adsorption temp is no more than 100 DEG C, and dipping adsorption time is 4-24h; Described baking temperature is 100-150 DEG C, and drying time is 1-6h; Described sintering temperature is 300-600 DEG C, and roasting time is 1-10h.
9. the preparation method of the catalyst as described in claim 5 or 6 or 7
In step (2), described nickel salt is the combination of in nickel nitrate, nickelous sulfate, nickel chloride, nickel acetate a kind or at least 2 kinds;
In step (2), described infusion process is equi-volume impregnating;
In step (2), described dipping adsorption temp is no more than 100 DEG C, and dipping adsorption time is 4-24h; Described baking temperature is 100-150 DEG C, and drying time is 1-6h; Described sintering temperature is 300-600 DEG C, and roasting time is 1-10h.
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| CN107033942A (en) * | 2017-06-09 | 2017-08-11 | 太原理工大学 | A kind of method that burnt catalytic gasification that gasifies is the richest in alkanisation |
| WO2018141648A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Iron-doped nickel methanation catalysts |
| WO2018141646A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Nickel methanation catalysts doped with iron and manganese |
| CN109453778A (en) * | 2018-10-08 | 2019-03-12 | 华南农业大学 | A kind of volcanic rock catalyst and its preparation method and application preparing methyl methanol syngas for biomass gasified gas |
| CN109626486A (en) * | 2018-12-29 | 2019-04-16 | 西安交通大学 | A kind of method of coupling processing high concentrated organic wastewater and heavy metal wastewater thereby |
| CN114574250A (en) * | 2022-04-14 | 2022-06-03 | 河南大学 | Method and device for preparing clean synthesis gas through biomass chemical-looping gasification |
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| CN106140168A (en) * | 2016-06-27 | 2016-11-23 | 北京华福工程有限公司 | The processing method of a kind of useless hydrogenation catalyst and the serosity prepared by described method |
| WO2018141648A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Iron-doped nickel methanation catalysts |
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| CN107033942A (en) * | 2017-06-09 | 2017-08-11 | 太原理工大学 | A kind of method that burnt catalytic gasification that gasifies is the richest in alkanisation |
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| CN109453778A (en) * | 2018-10-08 | 2019-03-12 | 华南农业大学 | A kind of volcanic rock catalyst and its preparation method and application preparing methyl methanol syngas for biomass gasified gas |
| CN109453778B (en) * | 2018-10-08 | 2021-07-09 | 华南农业大学 | Volcanic rock catalyst for preparing methanol synthesis gas from biomass gasification gas and preparation method and application thereof |
| CN109626486A (en) * | 2018-12-29 | 2019-04-16 | 西安交通大学 | A kind of method of coupling processing high concentrated organic wastewater and heavy metal wastewater thereby |
| CN114574250A (en) * | 2022-04-14 | 2022-06-03 | 河南大学 | Method and device for preparing clean synthesis gas through biomass chemical-looping gasification |
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