CN103706373A - Low-temperature high-activity methanation catalyst and preparation method thereof - Google Patents
Low-temperature high-activity methanation catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-temperature high-activity methanation catalyst and a preparation method thereof. The catalyst comprises metallic nickel as an active component, AL2O3 as a carrier and MgO as a structure auxiliary agent, and an appropriate amount of lanthanum oxide and manganese oxide are added as active auxiliary agents. The catalyst comprises the following main components in percentage by mass: 18-45% of NiO, 40-70% of Al2O3, 5-30% of MgO, 0.4-5% of La2O3 and 0.1-5% of MnO2. The catalyst disclosed by the invention has the advantages of large specific area, uniform nickel dispersity, good heat stability, strong oxidation resistance, low active temperature, adaptability to low hydrogen-carbon ratio and the like. The catalyst is applicable to preparation of LNG (liquefied natural gas) through methanation of industrial gases including coke oven gas, coal synthesis gas, semi coke exhaust gas and the like rich in CO, CO2 and H2, is particularly applicable to a methanation reaction in a low-temperature section, and can effectively improve the quality of synthetic natural gas. Meanwhile, the invention also provides the preparation method of the catalyst, and the preparation method is simple in process flow and can realize industrial production easily.
Description
Technical field
The invention belongs to methanation catalysis technical field, especially a kind of low temperature high activity methanation catalyst and preparation method thereof, particularly a kind of for high methane gas low concentration CO, CO
2the Catalysts and its preparation method of hydrogenation methanation.Industrial, this catalyst is applicable in the industrial gasses methanation LNG devices processed such as oven gas, producing synthesis gas from coal, blue charcoal tail gas, to improve the quality of synthetic natural gas.
Background technology
In recent years, China's natural gas market development is rapid, and insufficiency of supply-demand is increasing.It is just flourish that other industrial discharge gas such as domestic large moulded coal preparing natural gas, oven gas preparing natural gas are produced the unconventional Natural Gas Projects such as synthetic natural gas, constantly becomes the useful of China's natural gas industry and supplement.Wherein, the projects such as coke-oven gas methanation preparing liquefied natural gas (LNG), producing synthesis gas from coal LNG processed, because having clean environment firendly, capacity usage ratio advantages of higher, particularly receive publicity.In addition, after natural gas liquefaction, there is the features such as calorific value is high, performance good, storage and transportation space is little, can progressively replace vapour, diesel oil; Meanwhile, liquefied natural gas is conducive to realize national natural gas supply and regulates, and possesses significant energy supplementary result and economic benefit.
At present, natural gas liquefaction LNG processed is in the industrial cryogenic liquefying technology that all adopts.And the industrial gasses such as oven gas, producing synthesis gas from coal are rich in CO, CO
2if the methanation degree of depth is inadequate, residual CO
2enter after low-temperature liquefaction device as easy as rolling off a log freeze and occluding device and pipeline.According to cryogenics requirement, enter the CO of deep cooling operation
2content must be lower than 50 * 10
-6(volume ratio v/v, lower same), therefore, the industrial conversion performance to methanation catalyst is had higher requirement.
According to CO, CO
2methanation reaction principle formula (as follows):
CO + 3H
2 = CH
4 + H
2O -ΔH
Θ=206kJ/mol，
CO
2 + 4H
2 = CH
4 + 2H
2O -ΔH
Θ=165 kJ/mol。
Known methanation reaction is strong exothermal reaction, and therefore lower reaction temperature is more conducive to the carrying out of methanation.At present, the industrial multistage methanation process that adopt, to disperse reaction load, and coordinate efficient heat exchange to realize temperature control (for example ZL200910058611.0) more.But through multistage methanation, generally can only realize CO and transform completely, CO
2be converted into 0.5%～2% or following, meet national Natural gas standard one class gas requirement (GB17820-2012).As produce LNG, just need under low reaction temperature, pass through again low temperature high activity methanation catalyst by CO
2be converted into 50 * 10
-6(volume ratio v/v) is following or even lower, and low temperature also helps exploitation high-efficiency and energy-saving type technique simultaneously.
At present, both at home and abroad the research of Catalyst for Low-Temperature Methanation is mainly concentrated on ruthenium (Ru) base and two kinds of catalyst of nickel (Ni) base, although ruthenium catalyst has better low temperature active, due to expensive, do not there is industrial application value, so that extensively adopt or Ni is catalyst based.Yet the application of the Catalyst for Low-Temperature Methanation that the metallic nickel of take is active component is at present also in high hydrogen-carbon ratio (H
2/ (CO+CO
2)), on the application foundation of high activity temperature, low reaction air speed, and the heat resistance of this catalyst and non-oxidizability poor, a little less than resisting system fluctuation ability, narrow application range.As domestic synthesis ammonia system methanation catalyst, reactivity temperature is generally more than 300 ℃, H
2/ CO
2>=50, maximum operation (service) temperature is 450 ℃; Though the methanation catalyst that external Britain Davy company produces reports that its minimum Applicable temperature is 230 ℃, has no concrete data.
In addition, for making full use of the hydrogen energy source in the industrial gas such as oven gas, improve capacity usage ratio, methanation technology is also progressively to the future development of mending carbon or low hydrogen-carbon ratio.Therefore, Catalyst for Low-Temperature Methanation not only will meet outlet CO
2concentration is up to standard, but also needs to adapt to low hydrogen-carbon ratio, also needs to possess stronger heat resistance and non-oxidizability simultaneously.
Summary of the invention
The object of the invention is to: for the problem of above-mentioned existence, provide a kind of low temperature high activity methanation catalyst and preparation method thereof.The present invention is on the basis of existing patent of invention (ZL200810046429.9), the new methanation catalyst of exploitation.The catalyst of development has that specific surface is large, nickel is dispersed evenly, Heat stability is good, non-oxidizability is strong, active temperature is low and adapt to the advantages such as low hydrogen-carbon ratio, is a kind of for high methane gas low concentration CO, CO
2hydrogenation methanation catalyst, in the industrial gasses methanation LNG processed such as oven gas, producing synthesis gas from coal, blue charcoal tail gas, the particularly methanation of low-temperature zone, can effectively improve the quality of synthetic natural gas.
Another object of the present invention is to provide a kind of preparation method of above-mentioned low temperature high activity methanation catalyst.
To achieve these goals, the present invention adopts following technical scheme:
A low temperature high activity methanation catalyst, this catalyst comprises active component, carrier, structural promoter, coagent, wherein: nickel is active component, Al
2o
3for carrier, MgO is structural promoter, and rare earth lanthanum and manganese metal are as coagent;
Active component nickel is present in this catalyst with the form of NiO, and lanthanum and manganese are respectively with La
2o
3and MnO
2form be present in this catalyst;
The mass percent of each component is:
NiO 18%～45%，
Al
2O
3 40%～70%，
MgO 5%～30%，
La
2O
3 0.4%～5%，
MnO
2 0.1%～5%。
The mass percent of each component is:
NiO 20%～35%，
Al
2O
3 45%～65%，
La
2O
3 1.5%～4%，
MnO
2 1.5%～5%。
The preparation method of aforementioned low temperature high activity methanation catalyst, comprises the steps:
(1) auxiliary agent precipitation: the proportioning by carrier, active component, structural promoter, coagent in catalyst finished product takes respectively corresponding Al
2o
3carrier, Ni (NO
3)
26H
2o, magnesium salts, lanthanum salt, manganese salt (such as: by NiO, Al in catalyst finished product
2o
3, MgO, La
2o
3, MnO
2content, calculate corresponding Ni (NO
3)
26H
2o, Al
2o
3the quality of carrier, magnesium salts, lanthanum salt, manganese salt), take lanthanum salt and manganese salt as coagent salt.By the Al taking
2o
3carrier, magnesium salts are poured in the first isothermal reaction still, add again water and be mixed with dirty solution, by the dirty solution homogeneous heating to 60 in the first isothermal reaction still ℃～90 ℃, constantly stir dirty solution and slowly add precipitating reagent in dirty solution, isothermal reaction 2h～3h, until the pH of dirty solution value, it is 6.5～7.5 o'clock, stop reaction, obtain the first precipitation mixture, again the first precipitation mixture is filtered, the filter pulp after filtering is put into autoclave, at 180 ℃～220 ℃, process 10h～25h, obtain carrier intermediate, and the washing of carrier intermediate is extremely neutral.
(2) active constituent loading: by the Ni (NO taking
3)
26H
2o pours in the second reactor, in the second reactor, add water again, and stirring is warming up to 60 ℃～90 ℃, be configured to the nickel nitrate solution that density is 1.0g/ml～1.5 g/ml, again coagent salt is poured in the second reactor, form mixed solution, then step 1 washing to neutral carrier intermediate is poured in mixed solution, constant temperature stirs 0.5h～1h, in mixed solution, slowly add precipitating reagent to carry out precipitation reaction (active component is uniformly distributed in carrier with the form of subcarbonate) again, the precipitation reaction time is 1h～5h, in the second reactor, the pH value of solution is 6.5～7.5 o'clock, stop reaction, obtain the second precipitation mixture, by the second precipitation mixture successively after filtration, washing is to neutral, after dry, calcining at 400 ℃～500 ℃ again, sieve, obtain grained catalyst.
(3) moulding: in the grained catalyst obtaining to step 2, add the water of its quality 5%～15% and 3% ~ 5% lubricant, after mixing, compressing, obtain low temperature high activity methanation catalyst finished product.
In step 1, Al
2o
3carrier can be the Al that specific surface is larger
2o
3or porous Al (OH)
3in a kind of.As preferably, Al
2o
3carrier is porous Al (OH)
3.
In described step 1, magnesium salts is magnesium nitrate, and its chemical formula is Mg (NO
3)
26H
2o.
Described precipitating reagent is sodium carbonate liquor, and wherein the mass percent of sodium carbonate is 6%～9%.
In described step 3, lubricant is dolomol.
In described step 1, the wash temperature of carrier intermediate is 50 ℃～80 ℃; In described step 2, the second precipitation mixture successively after filtration, washing is to neutral, dry, and the temperature of washing is 50 ℃～80 ℃, and dry temperature is 90 ℃～150 ℃.
In described step 3, after mixing, compressing is cylindric, obtains low temperature high activity methanation catalyst finished product.
In described step 1, lanthanum salt is La (NO
3)
36H
2o, manganese salt is Mn (NO
3)
24H
2o.
Gained catalyst activity testing conditions of the present invention is as follows:
Reaction system temperature is 220 ℃～300 ℃, and pressure is 0.5MPa～4.0MPa, and unstripped gas air speed is 6000h
-1～15000h
-1time, feed gas volume content: CO
2: 0.2%～2.0%, H
2: 2.0%～23%, remaining CH
4: 85%～97.8%, by beds, measure its outlet tail gas content.
Compared with prior art, the present invention has following beneficial effect:
(1) pass through at the larger Al of specific surface
2o
3on carrier, precipitation applies auxiliary agent Mg, and through hydrothermal treatment consists, not only can obtain stable carrier structure, and has continued the porous of carrier, is conducive to the dispersion of active component nickel; In addition, hydrothermal treatment consists is impelled MgO and Al
2o
3thereby occur interacting makes carrier surface activity decreased, weakened the interaction between active component and carrier under high temperature, improved the heat resistance of catalyst;
(2) the present invention adopts step-by-step precipitation method, and it integrates the advantage of the precipitation method and infusion process, has not only greatly improved the nickel content of catalyst, also effectively increases the surperficial utilization rate of nickel;
(3) interpolation of coagent of the present invention has not only suppressed growing up of nickel crystallite, and has effectively improved the low temperature active of catalyst of the present invention.
Accompanying drawing explanation
Fig. 1 is the structural representation of gained catalyst activity determinator of the present invention.
Mark in figure: 1 is water tank, 2 is constant-flux pump, and 3 is wet flow indicator, and 4 is raw material gas cylinder, and 5 is hydrogen cylinder, and 6 is nitrogen cylinder, and 7 is evaporation preheater, and 8 is reactor, and 9 is temperature controller, and 10 is cooler, and 11 is pressure maintaining valve.
The specific embodiment
Below in conjunction with the specific embodiment, the present invention is described in further detail.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment.
In following embodiment, ppm represents volume content, is equal to 10
-6; Gas space velocity is all volume space velocity (GHSV).
In the present embodiment, require the constituent mass percentage of low temperature high activity methanation catalyst to be:
NiO：18%，Al
2O
3：70%，MgO：11.5%，La
2O
3：0.4%，MnO
2：0.1%。
Concrete preparation process is as follows.
A) auxiliary agent precipitation: take the porous Al (OH) that 214.33g crosses 300 eye mesh screens
3, and add 147.21g Mg (NO by proportioning
3)
26H
2o pours in the first isothermal reaction still.In the first isothermal reaction still, add 3000ml deionized water again, be configured to dirty solution.During by the dirty solution homogeneous heating to 70 in the first isothermal reaction still ℃, slowly adding concentration is 9% Na
2cO
3solution also constantly stirs, and keeps temperature-resistant, and reaction 2h, is 7.0 o'clock until the pH of dirty solution value, obtains carrier mixture.Carrier mixture is filtered again, the filter pulp after filtering is poured into polytetrafluoroethylene (PTFE) and does in the stainless steel autoclave of liner, sealing is processed 10h at 220 ℃, obtains carrier intermediate.Carrier intermediate is washed at 70 ℃ to neutral.
B) active constituent loading: take 140.10g Ni (NO by proportioning
3)
26H
2o, adds in the second reactor, adds water and stir to be warming up to 80 ℃, is configured to the nickel nitrate solution that density is 1.0g/ml, then adds 2.13g La (NO
3)
36H
2o and 0.58g Mn (NO
3)
24H
2o is dissolved in nickel nitrate solution, forms mixed solution.Step a washing to neutral carrier intermediate is poured in mixed solution, and constant temperature stirs 0.5h, then is 9% Na to slowly adding concentration in mixed solution
2cO
3solution carries out precipitation reaction, and the sedimentation time is 1h, treats that the pH value of solution in the second reactor is 7.5, obtains the second precipitation mixture.To react gained the second precipitation mixture successively after filtration, 70 ℃ of water washings to neutrality, then at 120 ℃ dry 3h, then put into Muffle furnace through 450 ℃ of calcining 2h, after grinding 200 mesh sieves, obtain grained catalyst.
C) shaping of catalyst: (that is: the quality of distilled water is grained catalyst 9% to add the distilled water of its quality 9% and the dolomol of its quality 5% in the grained catalyst obtaining to step b, the quality of dolomol be grained catalyst 5%), after mixing, compressing is the cylindric of Φ 3.5 * 3.5mm, obtains methanation catalyst finished product LTC-1.
In the present embodiment, require the constituent mass percentage of low temperature high activity methanation catalyst to be:
NiO：25%，Al
2O
3：40%，MgO：30%，La
2O
3：2%，MnO
2：3%。
Concrete preparation process is as follows.
A) auxiliary agent precipitation: take the porous Al (OH) that 122.48g crosses 300 eye mesh screens
3, and add 384.05g Mg (NO by proportioning
3)
26H
2o, pours in the first isothermal reaction still.In the first isothermal reaction still, add 3000ml deionized water again, be configured to dirty solution.During by the dirty solution homogeneous heating to 65 in the first isothermal reaction still ℃, slowly adding concentration is 9% Na
2cO
3solution also constantly stirs, and keeps temperature-resistant, and reaction 3h, is 6.5 o'clock until the pH of dirty solution value, obtains carrier mixture.Carrier mixture is filtered, filter pulp is poured into polytetrafluoroethylene (PTFE) and does in the stainless steel autoclave of liner again, and sealing is processed 25h at 180 ℃, obtains carrier intermediate.Carrier intermediate is washed at 70 ℃ to neutral.
B) active constituent loading: take 194.58g Ni (NO by proportioning
3)
26H
2o, adds in the second reactor, adds water and stir to be warming up to 70 ℃, is configured to the nickel nitrate solution that density is 1.5g/ml, then takes 10.63g La (NO
3)
36H
2o and 17.32g Mn (NO
3)
24H
2o is dissolved in nickel nitrate solution, forms mixed solution.Step a washing to neutral carrier intermediate is poured in mixed solution, and constant temperature stirs 0.5h, then is 6% Na to slowly adding concentration in mixed solution
2cO
3solution carries out precipitation reaction, and the sedimentation time is 2h, and in the second reactor, the pH value of solution is 7.5 o'clock, obtains the second precipitation mixture.To react gained the second precipitation mixture successively after filtration, 70 ℃ of water washings to neutrality, then at 120 ℃ dry 3h, then put into Muffle furnace through 450 ℃ of calcining 2h, after grinding 200 mesh sieves, obtain grained catalyst.
C) shaping of catalyst: add the distilled water of its quality 9% and the hard magnesium of its quality 3% in the grained catalyst obtaining to step b, after mixing, compressing is the cylindric of Φ 3.5 * 3.5mm, obtains methanation catalyst finished product LTC-2.
Embodiment 3
In the present embodiment, require the constituent mass percentage of low temperature high activity methanation catalyst to be:
NiO：35%，Al
2O
3：45%，MgO：15%，La
2O
3：2%，MnO
2：3%。
Concrete preparation process is as follows.
A) auxiliary agent precipitation: take the porous Al (OH) that 137.78g crosses 300 eye mesh screens
3, and add 192.00g Mg (NO by proportioning
3)
26H
2o, pours in the first isothermal reaction still.In the first isothermal reaction still, add 3000ml deionized water again, be configured to dirty solution.During by the dirty solution homogeneous heating to 70 in the first isothermal reaction still ℃, slowly adding concentration is 9% Na
2cO
3solution also constantly stirs, and keeps temperature-resistant, and reaction 2h, is 7.5 o'clock until the pH of dirty solution value, obtains carrier mixture.Carrier mixture is filtered, filter pulp is poured into polytetrafluoroethylene (PTFE) and does in the stainless steel autoclave of liner again, and sealing is processed 10h at 200 ℃, obtains carrier intermediate.Carrier intermediate is washed at 70 ℃ to neutral.
B) active constituent loading: take 272.41g Ni (NO by proportioning
3)
26H
2o, adds in the second reactor, adds water and stir to be warming up to 80 ℃, is configured to the nickel nitrate solution that density is 1.0g/ml, then takes 10.63g La (NO
3)
36H
2o and 17.32g Mn (NO
3)
24H
2o is dissolved in nickel nitrate solution, forms mixed solution.Step a washing to neutral carrier intermediate is poured in mixed solution, and constant temperature stirs 0.5h, then is 6% Na to slowly adding concentration in mixed solution
2cO
3solution carries out precipitation reaction, and the sedimentation time is 3h, and in the second reactor, the pH value of solution is 7.0 o'clock, obtains the second precipitation mixture.To react gained the second precipitation mixture successively after filtration, 70 ℃ of water washings to neutrality, then at 120 ℃ dry 3h, then put into Muffle furnace through 450 ℃ of calcining 2h, after grinding 200 mesh sieves, obtain grained catalyst.
C) shaping of catalyst: add the distilled water of its quality 9% and the dolomol of its quality 3% in the grained catalyst obtaining to step b, after mixing, compressing is the cylindric of Φ 3.5 * 3.5mm, obtains methanation catalyst finished product LTC-3.
Embodiment 4
In the present embodiment, require the constituent mass percentage of low temperature high activity methanation catalyst to be:
NiO：45%，Al
2O
3：40%，MgO：5%，La
2O
3：5%，MnO
2：5%。
Concrete preparation process is as follows.
A) auxiliary agent precipitation: take the Large ratio surface Al that 80.60g crosses 300 eye mesh screens
2o
3, and add 64.01g Mg (NO by proportioning
3)
26H
2o, pours in the first isothermal reaction still.In the first isothermal reaction still, add 3000ml deionized water again, be configured to dirty solution.When the dirty solution in the first isothermal reaction still is heated to 75 ℃, slowly adding concentration is 9% Na
2cO
3solution also constantly stirs, and keeps temperature-resistant, and reaction 1h, is 7.5 o'clock until the pH of dirty solution value, obtains carrier mixture.Carrier mixture is filtered, filter pulp is poured into polytetrafluoroethylene (PTFE) and does in the stainless steel autoclave of liner again, and sealing is processed 5h at 220 ℃, obtains carrier intermediate.Carrier intermediate is washed at 70 ℃ to neutral.
B) active constituent loading: take 350.24g Ni (NO by proportioning
3)
26H
2o, adds in the second reactor, adds water and stir to be warming up to 80 ℃, is configured to the nickel nitrate solution that density is 1.0g/ml, then takes 26.57g La (NO
3)
36H
2o and 28.85g Mn (NO
3)
24H
2o is dissolved in nickel nitrate solution, forms mixed solution.Step a washing to neutral carrier intermediate is poured in mixed solution, and constant temperature stirs 1h, then is 9% Na to slowly adding concentration in mixed solution
2cO
3solution carries out precipitation reaction, and the sedimentation time is 5h, and in the second reactor, the pH value of solution is 6.5 o'clock, obtains the second precipitation mixture.To react gained the second precipitation mixture successively after filtration, 70 ℃ of water washings to neutrality, then at 120 ℃ dry 3h, then put into Muffle furnace through 450 ℃ of calcining 2h, after grinding 200 mesh sieves, obtain grained catalyst.
C) shaping of catalyst: add the distilled water of its quality 9% and the dolomol of its quality 3% in the grained catalyst obtaining to step b, after mixing, compressing is the cylindric of Φ 3.5 * 3.5mm, obtains methanation catalyst finished product LTC-4.
(1) active appraisal experiment
Our department is divided into above-mentioned
embodiment 1～4the active appraisal experiment of preparing gained finished product Catalyst for Low-Temperature Methanation (remembering that respectively sample number is LTC-1, LTC-2, LTC-3, LTC-4).
The evaluation of catalyst adopts fixed bed reactors, and the methanation catalyst of preparing in the various embodiments described above is got respectively to 15ml, is loaded to the reaction tube of Φ 25 * 3.5mm, and beds ratio of height to diameter is 3.3, and concrete determination of activity device schematic diagram is shown in shown in accompanying drawing 1.
Analysis about Selection instrument is as follows:
1) gas-chromatography: U.S. Agilent GC-7820A, is mainly used to analyze unstripped gas and reactor outlet gas and forms;
2) infrared C O
2analyzer: the QGS-08B of Beijing BAIF-Maihak Analytical Instrument Co., Ltd., CO
2concentration analysis scope: 0ppm～50ppm, is mainly used to analyze the CO in outlet tail gas
2concentration.
Catalyst activity is measured with unstripped gas and is formed and see the following form shown in 1.
Table 1 determination of activity forms with unstripped gas
Determination of activity 1
First at 400 ℃ of temperature, with hydrogen pressure-raising, to 0.5MPa, go back protohydrogen air speed 2000h
-1, reductase 12 hour.Reduction finishes, and until system cooling, most after 220 ℃, passes into unstripped gas, and setting pressure is 1.5MPa, and unstripped gas air speed is 6000h
-1react, record analysis data after system stability 2h, the results are shown in following table 2.
Table 2 determination of activity 1 analytical data
As can be seen from Table 2, four kinds of catalyst of the present invention's development have good low temperature active when reaction temperature is 220 ℃.Within the specific limits, the increase of nickel content is conducive to the improvement of catalyst activity; In addition, it can also be seen that the adjustable extent of magnalium ratio in carrier is larger, coagent La
2o
3addition is 2%, MnO
2better while being 3%.
Determination of activity 2:
On the basis of determination of activity 1, system is lifted temperature to 240 ℃, pressure is that 1.5MPa is constant, and unstripped gas air speed is promoted to 10000h
-1react, record analysis data after system stability 2h, the results are shown in following table 3.
Table 3 determination of activity 2 analytical data
As can be seen from Table 3, four kinds of catalyst of the present invention's development have better low temperature active at 240 ℃, and can adapt to higher air speed (10000h
-1).Wherein LTC-3 sample has more outstanding performance.
Determination of activity 3:
On the basis of determination of activity 2, keeping system temperature is 240 ℃, and pressure is that 1.5MPa is constant, progressively unstripped gas air speed is slowly promoted to 15000h
-1react, record analysis data after system stability 2h, the results are shown in following table 4.
Table 4 determination of activity 3 analytical data
As can be seen from Table 4, four kinds of catalyst of the present invention's development have stable low temperature active at 240 ℃, and can adapt to higher reaction velocity (15000h
-1), but high-speed is to CO
2conversion ratio have a certain impact.Wherein the ability of LTC-3 sample adaptation condition fluctuation is stronger.
Determination of activity 4:
On the basis of determination of activity 3, system temperature is promoted to 300 ℃, keeping pressure is that 1.5MPa is constant, progressively unstripped gas air speed is slowly down to 10000h
-1react, record analysis data after system stability 2h, the results are shown in following table 5.
Table 5 determination of activity 4 analytical data
As can be seen from Table 5, four kinds of catalyst of the present invention's development still have good low temperature active in the time of 300 ℃.Wherein LTC-3 sample has more stable performance.
Determination of activity 5:
On the basis of determination of activity 4 by system N
2displacement, and by temperature increase to 680 ℃, heat-resisting operation 3h; Keeping pressure is that 1.5MPa is constant, then is cooled to 450 ℃, at N
2conveying under to pass into air speed be 2000 h
-1saturated steam 30min.After completing, turn back under the condition of determination of activity 3 and measure, reaction result is as following table 6.
Table 6 determination of activity 5 analytical data
Table 6 and table 3 are contrasted and can be found out, four kinds of catalyst of the present invention's development are after high-temperature heat-resistance, steam oxidation, and low temperature active is almost without large decay, and especially for LTC-3 sample, its heat endurance and antioxygenic property thereof are more excellent.
(2) physical and chemical performance characterizes
This part is chosen four kinds of catalyst samples that make in above-described embodiment and is carried out physical and chemical performance sign, this catalyst B of Main Analysis ET specific surface, pore volume, pore-size distribution etc.
Analytical instrument used: the NOVA2000e type n2 absorption apparatus that U.S.'s health tower instrument (Quantachrome) company produces.Analysis result sees the following form 7:
Table 7 surface analysis result
By table 7, can be seen, the prepared Catalyst for Low-Temperature Methanation of the present invention has larger specific surface and pore volume, and these features are all one of active high main reasons of catalyst reaction of the present invention.
Inventor also adopts above-mentioned experimental technique to carry out related assays to the methanation catalyst of other embodiment gained, finds that working as reaction system temperature is 220 ℃～300 ℃, and pressure is 0.5MPa～4.0MPa, and unstripped gas air speed is 6000h
-1～15000h
-1time, volume content is: CO
2: 0.2%～2.0%, H
2: 2.0%～23%, remaining CH
4: 85%～97.8% unstripped gas can make CO by methanation catalyst
2be converted into 3ppm～40ppm.Show that catalyst that the present invention makes has that specific surface is large, nickel is dispersed evenly really, Heat stability is good, non-oxidizability is strong, active temperature is low and adapt to the advantages such as low hydrogen-carbon ratio, applicable to oven gas, producing synthesis gas from coal, blue charcoal tail gas etc., is rich in CO, CO
2, H
2industrial gasses methanation LNG processed in, the particularly methanation of low-temperature zone, has great industrial application value.
The above embodiment is only the preferred embodiment for absolutely proving that the present invention lifts, and protection scope of the present invention is not limited to this.
Claims (9)
1. a low temperature high activity methanation catalyst, is characterized in that, this catalyst comprises active component, carrier, structural promoter and coagent, wherein: nickel is active component, Al
2o
3for carrier, MgO is structural promoter, and rare earth lanthanum and manganese metal are as coagent;
Active component nickel is present in this catalyst with the form of NiO, and lanthanum and manganese are respectively with La
2o
3and MnO
2form be present in this catalyst;
The mass percent of each component is:
NiO 18%～45%，
Al
2O
3 40%～70%，
MgO 5%～30%，
La
2O
3 0.4%～5%，
MnO
2 0.1%～5%。
2. low temperature high activity methanation catalyst according to claim 1, is characterized in that the mass percent of each component is:
NiO 20%～35%，
Al
2O
3 45%～65%，
MgO 10%～25%，
La
2O
3 1.5%～4%，
MnO
2 1.5%～5%。
3. according to the preparation method of low temperature high activity methanation catalyst described in claim 1～2 any one, comprise the steps:
(1) auxiliary agent precipitation: the proportioning by carrier, active component, structural promoter, coagent in catalyst finished product takes respectively corresponding Al
2o
3carrier, Ni (NO
3)
26H
2o, magnesium salts, lanthanum salt, manganese salt, take lanthanum salt and manganese salt as coagent salt, by the Al taking
2o
3carrier, magnesium salts are poured in the first isothermal reaction still, add again water and be mixed with dirty solution, by the dirty solution homogeneous heating to 60 in the first isothermal reaction still ℃～90 ℃, constantly stir dirty solution and slowly add precipitating reagent in dirty solution, isothermal reaction 2h～3h, until the pH of dirty solution value, it is 6.5～7.5 o'clock, stop reaction, obtain the first precipitation mixture, again the first precipitation mixture is filtered, the filter pulp after filtering is put into autoclave, at 180 ℃～220 ℃, process 10h～25h, obtain carrier intermediate, and the washing of carrier intermediate is extremely neutral;
(2) active constituent loading: by the Ni (NO taking
3)
26H
2o pours in the second reactor, in the second reactor, add water again, and stirring is warming up to 60 ℃～90 ℃, be configured to the nickel nitrate solution that density is 1.0g/ml～1.5g/ml, again coagent salt is poured in the second reactor, form mixed solution, then step 1 washing to neutral carrier intermediate is poured in mixed solution, constant temperature stirs 0.5h～1h, in mixed solution, slowly add precipitating reagent to carry out precipitation reaction again, the precipitation reaction time is 1h～5h, in the second reactor, the pH value of solution is 6.5～7.5 o'clock, stop reaction, obtain the second precipitation mixture, by the second precipitation mixture successively after filtration, washing is to neutral, after dry, calcining at 400 ℃～500 ℃ again, sieve, obtain grained catalyst,
(3) moulding: in the grained catalyst obtaining to step 2, add the water of its quality 5%～15% and 3%～5% lubricant, after mixing, compressing, obtain low temperature high activity methanation catalyst finished product.
4. the preparation method of low temperature high activity methanation catalyst according to claim 3, is characterized in that, in described step 1, magnesium salts is magnesium nitrate.
5. the preparation method of low temperature high activity methanation catalyst according to claim 3, is characterized in that, described precipitating reagent is sodium carbonate liquor, and wherein the mass percent of sodium carbonate is 6%～9%.
6. the preparation method of low temperature high activity methanation catalyst according to claim 3, is characterized in that, in described step 3, lubricant is dolomol.
7. the preparation method of low temperature high activity methanation catalyst according to claim 3, is characterized in that, in described step 1, the wash temperature of carrier intermediate is 50 ℃～80 ℃; In described step 2, the second precipitation mixture successively after filtration, washing is to neutral, dry, and the temperature of washing is 50 ℃～80 ℃, and dry temperature is 90 ℃～150 ℃.
8. the preparation method of low temperature high activity methanation catalyst according to claim 3, is characterized in that, in described step 3, after mixing, compressing is cylindric, obtains low temperature high activity methanation catalyst finished product.
9. according to the preparation method of low temperature high activity methanation catalyst described in claim 3-8 any one, it is characterized in that, in described step 1, lanthanum salt is La (NO
3)
36H
2o, manganese salt is Mn (NO
3)
24H
2o.
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