CN103706373B - A kind of Low-temperature high-activity methanation catalyst and preparation method thereof - Google Patents
A kind of Low-temperature high-activity methanation catalyst and preparation method thereof Download PDFInfo
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- CN103706373B CN103706373B CN201310726214.2A CN201310726214A CN103706373B CN 103706373 B CN103706373 B CN 103706373B CN 201310726214 A CN201310726214 A CN 201310726214A CN 103706373 B CN103706373 B CN 103706373B
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Abstract
The invention discloses a kind of Low-temperature high-activity methanation catalyst and preparation method thereof.This catalyst take metallic nickel as active component, Al
2o
3for carrier, MgO is structural promoter, and adds appropriate lanthana and manganese oxide as coagent; Its key component mass percent is respectively: NiO:18% ~ 45%, Al
2o
3: 40% ~ 70%, MgO:5% ~ 30%, La
2o
3: 0.4% ~ 5%, MnO
2: 0.1% ~ 5%.Catalyst of the present invention has that specific surface is large, nickel is dispersed evenly, Heat stability is good, non-oxidizability are strong, active temperature is low and adapt to the advantages such as low hydrogen-carbon ratio.Be applicable to oven gas, producing synthesis gas from coal, blue charcoal tail gas etc. and be rich in CO, CO
2, H
2industrial gasses methanation LNG in, be particularly useful for the methanation reaction of low-temperature zone, effectively can improve the quality of synthetic natural gas.Meanwhile, the present invention also provides the preparation method of this catalyst, and this method technological process is simple, is easy to realize suitability for industrialized production.
Description
Technical field
The invention belongs to methanation catalyst technical field, especially a kind of Low-temperature high-activity methanation catalyst and preparation method thereof, particularly one is used for low concentration CO, CO in high methane gas
2the Catalysts and its preparation method of hydrogenation methanation.Industrially, this catalyst is applicable in the industrial gasses methanation LNG devices 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 produce the Unconventional forage projects such as synthetic natural gas, constantly becomes the useful supplement of China's natural gas industry.Wherein, the projects such as coke-oven gas methanation preparing liquefied natural gas (LNG), producing synthesis gas from coal LNG, because having clean environment firendly, capacity usage ratio advantages of higher, particularly receive publicity.In addition, there is after natural gas liquefaction the features such as calorific value is high, performance good, storage and transportation space is little, progressively can replace vapour, diesel oil; Meanwhile, liquefied natural gas is conducive to realizing national natural gas supply and regulates, and possesses significant energy supplementary result and economic benefit.
At present, natural gas liquefaction LNG industrially all adopts cryogenic liquefying technology.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
2after entering 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 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 multistage methanation process of industrial many employings, to disperse to react load, and coordinates efficient heat exchange to control (such as ZL200910058611.0) to realize temperature.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 produced LNG, just to need under low reaction temperature again by Low-temperature high-activity methanation catalyst by CO
2be converted into 50 × 10
-6(volume ratio v/v) below or even lower, low temperature also helps exploitation high-efficiency and energy-saving type technique simultaneously.
At present, mainly concentrate on ruthenium (Ru) base and nickel (Ni) base two kinds of catalyst, although ruthenium catalyst has better low temperature active, due to expensive to the research of Catalyst for Low-Temperature Methanation both at home and abroad, not there is industrial application value, so that extensively adopt or Ni is catalyst based.But, be that the application of the Catalyst for Low-Temperature Methanation of active component is also in high hydrogen-carbon ratio (H at present with metallic nickel
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, resist system fluctuation ability weak, narrow application range.As domestic synthesis ammonia system methanation catalyst, reactivity temperature generally more than 300 DEG C, H
2/ CO
2>=50, maximum operation (service) temperature is 450 DEG C; Though the methanation catalyst that Davy company of external Britain produces reports that its minimum Applicable temperature is 230 DEG C, have 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 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 need 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 above-mentioned Problems existing, a kind of Low-temperature high-activity methanation catalyst and preparation method thereof is provided.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 are strong, active temperature is low and adapt to the advantages such as low hydrogen-carbon ratio, is a kind of for low concentration CO, CO in high methane gas
2hydrogenation methanation catalyst, be applicable in the industrial gasses methanation LNG such as oven gas, producing synthesis gas from coal, blue charcoal tail gas, the particularly methanation of low-temperature zone, effectively can 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 kind of 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
340%～70%，
MgO 5%～30%，
La
2O
30.4%～5%，
MnO
20.1%～5%。
The mass percent of each component is:
NiO 20%～35%，
Al
2O
345%～65%，
MgO 10%～25%，
La
2O
31.5%～4%，
MnO
21.5%～5%。
The preparation method of aforementioned Low-temperature high-activity methanation catalyst, comprises the steps:
(1) auxiliary agent precipitation: take corresponding Al respectively by the proportioning of carrier, active component, structural promoter, coagent in finished catalyst
2o
3carrier, Ni (NO
3)
26H
2o, magnesium salts, lanthanum salt, manganese salt are (such as: by NiO, Al in finished catalyst
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), with lanthanum salt and manganese salt for coagent salt.By the Al taken
2o
3carrier, magnesium salts are poured in the first isothermal reaction still, add water again and be mixed with dirty solution, by the dirty solution homogeneous heating to 60 in the first isothermal reaction still DEG C ~ 90 DEG C, continuous stirring dirty solution also slowly adds precipitating reagent in dirty solution, isothermal reaction 2h ~ 3h, when the pH value of dirty solution is 6.5 ~ 7.5, stop reaction, obtain the first precipitation mixture, again the first precipitation mixture is filtered, autoclave is put in the filter pulp after filtering, at 180 DEG C ~ 220 DEG C, processes 10h ~ 25h, obtain carrier intermediate, and by the washing of carrier intermediate to neutral.
(2) active constituent loading: by the Ni (NO taken
3)
26H
2o pours in the second reactor, add water in the second reactor again, and stirring is warming up to 60 DEG C ~ 90 DEG C, 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 carrier intermediate step 1 washed to neutrality is poured in mixed solution, constant temperature stirs 0.5h ~ 1h, in mixed solution, slowly add precipitating reagent again carry out precipitation reaction (active component is uniformly distributed in carrier with the form of subcarbonate), the precipitation reaction time is 1h ~ 5h, when in the second reactor, the pH value of solution is 6.5 ~ 7.5, stop reaction, obtain the second precipitation mixture, by the second precipitation mixture successively after filtration, washing is to neutral, after drying, calcine at 400 DEG C ~ 500 DEG C again, sieve, obtain grained catalyst.
(3) shaping: in the grained catalyst that step 2 obtains, to add the water of its quality 5% ~ 15% and the lubricant of 3% ~ 5%, after mixing, compressing, namely obtain Low-temperature high-activity methanation catalyst finished product.
In step 1, Al
2o
3carrier can be the larger Al of specific surface
2o
3or porous Al (OH)
3in one.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 DEG C ~ 80 DEG C; In described step 2, the second precipitation mixture successively after filtration, washing to neutral, dry, the temperature of washing is 50 DEG C ~ 80 DEG C, and dry temperature is 90 DEG C ~ 150 DEG C.
In described step 3, after mixing, compressing is cylindric, namely 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 DEG C ~ 300 DEG C, 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%, measure its outlet tail gas content by beds.
Compared with prior art, the present invention has following beneficial effect:
(1) pass through at the larger Al of specific surface
2o
3precipitation coating auxiliary agent Mg on carrier, and through hydrothermal treatment consists, not only stable carrier structure can be obtained, and continued the porous of carrier, be conducive to the dispersion of active component nickel; In addition, hydrothermal treatment consists impels MgO and Al
2o
3occur interact thus carrier surfactant is reduced, weaken the interaction between active component and carrier under high temperature, improve 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, not only substantially increases the nickel content of catalyst, also effectively increases the surface utilisation of nickel;
(3) interpolation of coagent of the present invention not only inhibits growing up of nickel crystallite, and effectively improves 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, and 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, 7 is evaporation preheater, and 8 is reactor, and 9 is temperature controller, and 10 is cooler, and 11 is pressure maintaining valve.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in further detail.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment.
In following embodiment, ppm represents volume content, is equal to 10
-6; Gas space velocity is all volume space velocity (GHSV).
Embodiment 1
Require in the present embodiment that the constituent mass percentage of Low-temperature high-activity methanation catalyst is:
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 dirty solution homogeneous heating to 70 DEG C in the first isothermal reaction still, slowly add the Na that concentration is 9%
2cO
3solution also constantly stirs, and keeps temperature-resistant, and reaction 2h, when the pH value of dirty solution is 7.0, obtains carrier mixture.Filtered by carrier mixture, the filter pulp after filtration is poured into polytetrafluoroethylene (PTFE) and does in the stainless steel autoclave of liner, sealing, processes 10h, obtains carrier intermediate at 220 DEG C.Carrier intermediate is washed at 70 DEG C 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 DEG C, 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.Pour in mixed solution by step a washing to neutral carrier intermediate, constant temperature stirs 0.5h, then in mixed solution, slowly add the Na that concentration is 9%
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 second precipitation mixture successively after filtration, after 70 DEG C of water washings to neutrality, then at 120 DEG C dry 3h, then put into Muffle furnace through 450 DEG C of calcining 2h, cross 200 mesh sieves after grinding, obtain grained catalyst.
C) shaping of catalyst: (that is: the quality of distilled water is 9% of grained catalyst to add the dolomol of the distilled water of its quality 9% and its quality 5% in the grained catalyst that step b obtains, the quality of dolomol is 5% of grained catalyst), after mixing, compressing is the cylindric of Φ 3.5 × 3.5mm, namely obtains methanation catalyst finished product LTC-1.
Embodiment 2
Require in the present embodiment that the constituent mass percentage of Low-temperature high-activity methanation catalyst is:
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 dirty solution homogeneous heating to 65 DEG C in the first isothermal reaction still, slowly add the Na that concentration is 9%
2cO
3solution also constantly stirs, and keeps temperature-resistant, and reaction 3h, when the pH value of dirty solution is 6.5, obtains carrier mixture.Filtered by carrier mixture, filter pulp is poured into polytetrafluoroethylene (PTFE) and does in the stainless steel autoclave of liner again, and sealing, processes 25h, obtain carrier intermediate at 180 DEG C.Carrier intermediate is washed at 70 DEG C 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 DEG C, 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.Pour in mixed solution by step a washing to neutral carrier intermediate, constant temperature stirs 0.5h, then in mixed solution, slowly add the Na that concentration is 6%
2cO
3solution carries out precipitation reaction, and the sedimentation time is 2h, when the pH value of solution is 7.5 in the second reactor, obtains the second precipitation mixture.To react gained second precipitation mixture successively after filtration, after 70 DEG C of water washings to neutrality, then at 120 DEG C dry 3h, then put into Muffle furnace through 450 DEG C of calcining 2h, cross 200 mesh sieves after grinding, 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 that step b obtains, after mixing, compressing is the cylindric of Φ 3.5 × 3.5mm, namely obtains methanation catalyst finished product LTC-2.
Embodiment 3
Require in the present embodiment that the constituent mass percentage of Low-temperature high-activity methanation catalyst is:
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 dirty solution homogeneous heating to 70 DEG C in the first isothermal reaction still, slowly add the Na that concentration is 9%
2cO
3solution also constantly stirs, and keeps temperature-resistant, and reaction 2h, when the pH value of dirty solution is 7.5, obtains carrier mixture.Filtered by carrier mixture, filter pulp is poured into polytetrafluoroethylene (PTFE) and does in the stainless steel autoclave of liner again, and sealing, processes 10h, obtain carrier intermediate at 200 DEG C.Carrier intermediate is washed at 70 DEG C 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 DEG C, 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.Pour in mixed solution by step a washing to neutral carrier intermediate, constant temperature stirs 0.5h, then in mixed solution, slowly add the Na that concentration is 6%
2cO
3solution carries out precipitation reaction, and the sedimentation time is 3h, when the pH value of solution is 7.0 in the second reactor, obtains the second precipitation mixture.To react gained second precipitation mixture successively after filtration, after 70 DEG C of water washings to neutrality, then at 120 DEG C dry 3h, then put into Muffle furnace through 450 DEG C of calcining 2h, cross 200 mesh sieves after grinding, 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 that step b obtains, after mixing, compressing is the cylindric of Φ 3.5 × 3.5mm, namely obtains methanation catalyst finished product LTC-3.
Embodiment 4
Require in the present embodiment that the constituent mass percentage of Low-temperature high-activity methanation catalyst is:
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 dirty solution in first isothermal reaction still is heated to 75 DEG C, slowly add the Na that concentration is 9%
2cO
3solution also constantly stirs, and keeps temperature-resistant, and reaction 1h, when the pH value of dirty solution is 7.5, obtains carrier mixture.Filtered by carrier mixture, filter pulp is poured into polytetrafluoroethylene (PTFE) and does in the stainless steel autoclave of liner again, and sealing, processes 5h, obtain carrier intermediate at 220 DEG C.Carrier intermediate is washed at 70 DEG C 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 DEG C, 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.Pour in mixed solution by step a washing to neutral carrier intermediate, constant temperature stirs 1h, then in mixed solution, slowly add the Na that concentration is 9%
2cO
3solution carries out precipitation reaction, and the sedimentation time is 5h, when the pH value of solution is 6.5 in the second reactor, obtains the second precipitation mixture.To react gained second precipitation mixture successively after filtration, after 70 DEG C of water washings to neutrality, then at 120 DEG C dry 3h, then put into Muffle furnace through 450 DEG C of calcining 2h, cross 200 mesh sieves after grinding, 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 that step b obtains, after mixing, compressing is the cylindric of Φ 3.5 × 3.5mm, namely obtains methanation catalyst finished product LTC-4.
(1) active appraisal experiment
Our department is divided into above-mentioned
embodiment 1 ~ 4prepare the active appraisal experiment of gained finished product Catalyst for Low-Temperature Methanation (remembering that sample number is LTC-1, LTC-2, LTC-3, LTC-4 respectively).
The evaluation of catalyst adopts fixed bed reactors, and the methanation catalyst prepared in the various embodiments described above is got 15ml respectively, is loaded to the reaction tube of Φ 25 × 3.5mm, 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 composition;
2) infrared C O
2analyzer: Beijing BAIF-Maihak Analytical Instrument Co., Ltd. QGS-08B, CO
2concentration analysis scope: 0ppm ~ 50ppm, is mainly used to analyze the CO in outlet tail gas
2concentration.
Catalyst activity mensuration unstripped gas composition sees the following form shown in 1.
Table 1 determination of activity unstripped gas forms
Determination of activity 1
First, at temperature 400 DEG C, with hydrogen pressure-raising to 0.5MPa, protohydrogen air speed 2000h is gone back
-1, reductase 12 hour.Reduction terminates, and after system cooling most 220 DEG C, pass into unstripped gas, 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 DEG C.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 comparatively large, coagent La
2o
3addition is 2%, MnO
2better when being 3%.
Determination of activity 2:
System is lifted temperature to 240 DEG C by the basis of determination of activity 1, and 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 DEG C, 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 DEG C, 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 DEG C, 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:
System temperature is promoted to 300 DEG C by the basis of determination of activity 3, keeps pressure to be 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 300 DEG C time.Wherein LTC-3 sample has more stable performance.
Determination of activity 5:
By system N on the basis of determination of activity 4
2displacement, and by temperature increase to 680 DEG C, heat-resisting operation 3h; Keep pressure to be that 1.5MPa is constant, then be cooled to 450 DEG C, at N
2conveying under to pass into air speed be 2000 h
-1saturated steam 30min.After completing, measure under turning back to the condition of determination of activity 3, reaction result is as following table 6.
Table 6 determination of activity 5 analytical data
Table 6 and table 3 are carried out contrast can find out, the present invention development four kinds of catalyst after high-temperature heat-resistance, steam oxidation, low temperature active almost without large decay, especially for LTC-3 sample, its heat endurance and antioxygenic property more excellent.
(2) physical and chemical performance characterizes
This part is chosen four kinds of catalyst samples obtained in above-described embodiment and is carried out physical and chemical performance sign, Main Analysis these catalyst B ET specific surface, pore volume, pore-size distribution etc.
Analytical instrument used: the NOVA2000e type n2 absorption apparatus that health tower instrument (Quantachrome) company of the U.S. produces.Analysis result sees the following form 7:
Table 7 surface analysis result
Can be seen by table 7, the Catalyst for Low-Temperature Methanation obtained by 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 pressure is 0.5MPa ~ 4.0MPa, and unstripped gas air speed is 6000h when reaction system temperature is 220 DEG C ~ 300 DEG C
-1~ 15000h
-1time, volume content is: CO
2: 0.2% ~ 2.0%, H
2: 2.0% ~ 23%, remaining CH
4: the unstripped gas of 85% ~ 97.8% can make CO by methanation catalyst
2be converted into 3ppm ~ 40ppm.Show that catalyst that the present invention obtains has that specific surface is large, nickel is dispersed evenly, Heat stability is good, non-oxidizability are strong, active temperature is low and adapt to the advantages such as low hydrogen-carbon ratio really, is applicable to oven gas, producing synthesis gas from coal, blue charcoal tail gas etc. and is rich in CO, CO
2, H
2industrial gasses methanation LNG in, the particularly methanation of low-temperature zone, has great commercial introduction using value.
The above embodiment is only that protection scope of the present invention is not limited thereto in order to absolutely prove the preferred embodiment that the present invention lifts.
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
340%～70%，
MgO 5%～30%，
La
2O
30.4%～5%，
MnO
20.1%～5%；
Described catalyst adopts the method comprised the steps to be prepared from:
(1) auxiliary agent precipitation: take corresponding Al respectively by the proportioning of carrier, active component, structural promoter, coagent in finished catalyst
2o
3carrier, Ni (NO
3)
26H
2o, magnesium salts, lanthanum salt, manganese salt, with lanthanum salt and manganese salt for coagent salt, by the Al taken
2o
3carrier, magnesium salts are poured in the first isothermal reaction still, add water again and be mixed with dirty solution, by the dirty solution homogeneous heating to 60 in the first isothermal reaction still DEG C ~ 90 DEG C, continuous stirring dirty solution also slowly adds precipitating reagent in dirty solution, isothermal reaction 2h ~ 3h, when the pH value of dirty solution is 6.5 ~ 7.5, stop reaction, obtain the first precipitation mixture, again the first precipitation mixture is filtered, autoclave is put in the filter pulp after filtering, at 180 DEG C ~ 220 DEG C, processes 10h ~ 25h, obtain carrier intermediate, and by the washing of carrier intermediate to neutral;
(2) active constituent loading: by the Ni (NO taken
3)
26H
2o pours in the second reactor, add water in the second reactor again, and stirring is warming up to 60 DEG C ~ 90 DEG C, 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 carrier intermediate step 1 washed to neutrality is poured in mixed solution, constant temperature stirs 0.5h ~ 1h, in mixed solution, slowly add precipitating reagent again carry out precipitation reaction, the precipitation reaction time is 1h ~ 5h, when in the second reactor, the pH value of solution is 6.5 ~ 7.5, stop reaction, obtain the second precipitation mixture, by the second precipitation mixture successively after filtration, washing is to neutral, after drying, calcine at 400 DEG C ~ 500 DEG C again, sieve, obtain grained catalyst,
(3) shaping: in the grained catalyst that step 2 obtains, to add the water of its quality 5% ~ 15% and the lubricant of 3% ~ 5%, after mixing, compressing, namely obtain Low-temperature high-activity methanation catalyst finished product.
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
345%～65%，
MgO 10%～25%，
La
2O
31.5%～4%，
MnO
21.5%～5%。
3. the preparation method of Low-temperature high-activity methanation catalyst according to any one of claim 1 ~ 2, comprises the steps:
(1) auxiliary agent precipitation: take corresponding Al respectively by the proportioning of carrier, active component, structural promoter, coagent in finished catalyst
2o
3carrier, Ni (NO
3)
26H
2o, magnesium salts, lanthanum salt, manganese salt, with lanthanum salt and manganese salt for coagent salt, by the Al taken
2o
3carrier, magnesium salts are poured in the first isothermal reaction still, add water again and be mixed with dirty solution, by the dirty solution homogeneous heating to 60 in the first isothermal reaction still DEG C ~ 90 DEG C, continuous stirring dirty solution also slowly adds precipitating reagent in dirty solution, isothermal reaction 2h ~ 3h, when the pH value of dirty solution is 6.5 ~ 7.5, stop reaction, obtain the first precipitation mixture, again the first precipitation mixture is filtered, autoclave is put in the filter pulp after filtering, at 180 DEG C ~ 220 DEG C, processes 10h ~ 25h, obtain carrier intermediate, and by the washing of carrier intermediate to neutral;
(2) active constituent loading: by the Ni (NO taken
3)
26H
2o pours in the second reactor, add water in the second reactor again, and stirring is warming up to 60 DEG C ~ 90 DEG C, 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 carrier intermediate step 1 washed to neutrality is poured in mixed solution, constant temperature stirs 0.5h ~ 1h, in mixed solution, slowly add precipitating reagent again carry out precipitation reaction, the precipitation reaction time is 1h ~ 5h, when in the second reactor, the pH value of solution is 6.5 ~ 7.5, stop reaction, obtain the second precipitation mixture, by the second precipitation mixture successively after filtration, washing is to neutral, after drying, calcine at 400 DEG C ~ 500 DEG C again, sieve, obtain grained catalyst,
(3) shaping: in the grained catalyst that step 2 obtains, to add the water of its quality 5% ~ 15% and the lubricant of 3% ~ 5%, after mixing, compressing, namely obtain Low-temperature high-activity methanation catalyst finished product.
4. the preparation method of Low-temperature high-activity methanation catalyst according to claim 3, it 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, in described step 1 and step 2, 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, it 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, it is characterized in that, in described step 1, the wash temperature of carrier intermediate is 50 DEG C ~ 80 DEG C; In described step 2, the second precipitation mixture successively after filtration, washing to neutral, dry, the temperature of washing is 50 DEG C ~ 80 DEG C, and dry temperature is 90 DEG C ~ 150 DEG C.
8. the preparation method of Low-temperature high-activity methanation catalyst according to claim 3, it is characterized in that, in described step 3, after mixing, compressing is cylindric, namely obtains Low-temperature high-activity methanation catalyst finished product.
9. the preparation method of Low-temperature high-activity methanation catalyst according to any one of claim 3-8, 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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| CN107335449B (en) * | 2017-07-24 | 2020-04-17 | 西南化工研究设计院有限公司 | Composite component methanation catalyst and preparation method thereof |
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