CN103480375A - Carbon monoxide methanating catalyst and preparation method thereof - Google Patents

Carbon monoxide methanating catalyst and preparation method thereof Download PDF

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Publication number
CN103480375A
CN103480375A CN201310454106.4A CN201310454106A CN103480375A CN 103480375 A CN103480375 A CN 103480375A CN 201310454106 A CN201310454106 A CN 201310454106A CN 103480375 A CN103480375 A CN 103480375A
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China
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catalyst
carbon monoxide
methanation
characterized
preparation method
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CN201310454106.4A
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Chinese (zh)
Inventor
詹瑛瑛
辜冬梅
陈崇启
郑起
魏可镁
林性怡
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福州大学
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Abstract

The invention discloses a carbon monoxide methanating catalyst with high hydrothermal stability and a preparation method thereof, and belongs to the technical field of preparation of catalysts. The carbon monoxide methanating catalyst is prepared mainly by a co-precipitation method according to the following steps: taking alumina (Al2O3) as a carrier and metal nickel as an active component, adding Zr and transition metals as additives, uniformly mixing salt solutions, precipitating, aging, performing suction filtration, washing, drying and calcining the mixture. The preparation method is simple; raw materials are easily available; the cost is low; and the prepared catalyst has the characteristics of high specific surface area, large pore volume and concentrated pore size distribution, is applicable to hydrogenation reactions, in particular to methanation reaction of high-concentration carbon monoxide, and has the advantages of wide using temperature range, high catalytic activity, high hydrothermal stability and the like.

Description

A kind of the methanation of carbon monoxide Catalysts and its preparation method

Technical field

The invention belongs to catalyst preparation technical field, be specifically related to a kind of the methanation of carbon monoxide Catalysts and its preparation method with high hydrothermal stability.

Background technology

The characteristics of the energy general layout of China are " oil starvation, weak breath, rich coals ".This resource structures causes China's natural gas market to have serious disparities between supply and demand, and Development of Coal preparing natural gas technology is significant to guaranteeing Chinese energy safety.Much experts think, coal preparing natural gas energy transformation ratio is than coal methyl alcohol processed, dimethyl ether, and coal liquefaction energy transformation ratio is high, and water consumption is low.The synthesis gas that coal gasification makes, contain a large amount of carbon monoxide and hydrogen, and its methanation is prepared to the methane combustion gas, is considered to produce a kind of simple high effective way of high heat value gas, has potential industry widely and commercial value.The synthesis gas methanation relates generally to following reaction:

Methanation is the last one exothermic process, and oxide carrier heat conductivility commonly used is poor, easily forms in course of reaction " focus ", and causes sintering and the deactivation phenomenom of catalyst.Therefore, the emphasis of the research of the methanation of carbon monoxide mainly concentrates on the active catalyst high, that selectively good and stability is strong of preparation.

The domestic development of having carried out very early methanation catalyst, purify removing of a small amount of CO in ammonia synthesis process or fuel cell but be mainly used in, and in these techniques, CO concentration is low, and the methanation load is little, and these are different from carbonomonoxide concentration situation higher in synthesis gas.For high CO concentration system, methanation produces large water gaging, and some reaction process are even introduced water in course of reaction and brought the load of equipment to alleviate the strong heat release of methanation.Therefore, high hydrothermal stability is to ensure that the high concentration the methanation of carbon monoxide System Catalyst such as coal preparing natural gas has long-life key element.Yet bright to the investigation of catalyst hydrothermal stability is report.At present, the preparing methane from coal catalyst preparation technology is still mainly grasped Denmark Topsoe company, under Britain Johnson Matthey in the external major company such as Davy company, ICI company, German BASF AG hand.The CGR methanation catalyst of Davy company is nickel catalyst, more than nickel content 50 %.CN101391218B discloses a kind of MgO-Al 2o 3complex carrier dip loading Ni is catalyst based for gas employing methanation of coke oven.CN1012389826A discloses a kind of preparation method for the gas employing methanation of coke oven catalyst, and carrier is the g-aluminium oxide, synthetic containing NiO, CeO by the heating using microwave solid phase 2catalyst with SiC; CN102513124A discloses that to take g-aluminium oxide or titanium dioxide be carrier, by deposition-precipitation method load active component Ni and auxiliary agent La and Sr, Mn, Zr, prepares gas employing methanation of coke oven Ni catalyst based.

The methanation catalyst of above-mentioned introduction or exist nickel content high, or have the cost technology problems such as complicated process of preparation.

To sum up, find that catalytic activity is high, good hydrothermal stability and the simple catalyst of preparation technology become the key problem that current high-concentration carbon monoxide methanation technology need to solve.

Summary of the invention

The object of the invention is to situation and deficiency for prior art, with aluminium oxide (Al 2o 3) be carrier, take metallic nickel as active component, add Zr and transition metal as auxiliary agent, adopt coprecipitation make a kind of have use that wide temperature region, catalytic activity are high, the methanation of carbon monoxide catalyst of good hydrothermal stability.

For achieving the above object, the present invention adopts following technical scheme:

A kind of the methanation of carbon monoxide catalyst is with Al 2o 3for carrier, Ni is active component, improves catalytic activity and the hydrothermal stability of catalyst by adding Zr and transition metal;

The percentage by weight of finished catalyst consists of:

Nickel 12-18 %

Transition metal 0-5 %

Zirconia 0-20 %

Aluminium oxide 65-88 %

The mass percent sum of each component is 100%.

Described transition metal is one or both in Fe, Co, Mn.

The specific area of described catalyst is 150-200 m 2/ g, pore volume is 0.35-0.45 cm 3/ g, average pore size is 9.2-11.2 nm.

The method for preparing the methanation of carbon monoxide catalyst as above comprises the following steps:

(1) by the soluble-salt of nickel, aluminium, zirconium and transition metal and dispersant wiring solution-forming, with alkali lye, as precipitating reagent, at 40-80 ℃, pH value, be to carry out neutralization precipitation under 8-10, aging 6-24 h then;

(2) sediment to pH<7, in 80-110 ℃ of dry 6-12 h, then, through 350-950 ℃ of roasting 1-6 h, makes described the methanation of carbon monoxide catalyst by the deionized water filtering and washing.

The described soluble-salt of step (1) is sulfate, nitrate, acetate or chlorate.Dispersant is a kind of in polyethylene glycol, polyacrylic acid, APEO, Arabic gum, laurate.Precipitating reagent is one or more in NaOH, potassium hydroxide, sodium carbonate, potash, ammonium carbonate, carbonic hydroammonium, ammoniacal liquor.

Remarkable advantage of the present invention is:

(1) each constitutive material of catalyst of the present invention is easy to get, and cheap, the preparation method is simple.

(2) catalyst of the present invention has high-specific surface area, large pore volume, the concentrated characteristics of pore-size distribution, adapts to the high-speed service condition.

(3) catalyst of the present invention supports when low in active component nickel, still has very high catalytic activity, can reduce the catalyst cost.

(4) catalyst of the present invention, by adding auxiliary agent and controlling preparation parameter, make catalyst have catalytic activity and the hydrothermal stability of excellent the methanation of carbon monoxide.After 800 ℃ of hydrothermal treatment consists 10 h, at 40000 mLh -1g -1high-quality air speed condition under, in the time of 340 ℃, the CO conversion ratio is higher than 90 %.

The accompanying drawing explanation

X-ray diffractogram after Fig. 1 catalyst (b) reduction that to be the catalyst (a) that obtains of the embodiment of the present invention 2 obtain with comparative example 1.

The graph of pore diameter distribution that Fig. 2 is the catalyst that obtains of various embodiments of the present invention.

Fig. 3 be the catalyst that obtains of the embodiment of the present invention 3 after hydrothermal treatment consists, the CO methanation activity evaluation result at the differential responses temperature.

The transmission electron microscope picture that Fig. 4 is the catalyst that obtains of the embodiment of the present invention 3.

The specific embodiment

For the ease of understanding the present invention, below in conjunction with accompanying drawing, embodiment, the methanation of carbon monoxide catalyst the present invention relates to is further described, but the present invention also not only is confined to these embodiment.

Embodiment 1:

Take respectively Ni (NO 3) 26H 2o, Al (NO 3) 39H 2o, Mn (NO 3) 2, Zr (NO 3) 45H 2o and dispersant A 3.613 g, 30.464 g, 1.112 g, 3.345 g, 0.3 g are made into 200 mL solution, as precipitating reagent, carry out co-precipitation with NaOH under 40 ℃, controlling pH is 8-10, after completing, 1 h is stirred in continuation, then standing aging 16 h.The gained sediment is filtered, 90 ℃ of drying 12 h, 700 ℃ of roasting 4 h, obtain catalyst.

Embodiment 2:

Take respectively Ni (NO 3) 26H 2o, Al (NO 3) 39H 2o, Fe (NO 3) 39H 2o, Zr (NO 3) 45H 2o and dispersant B 4.954g, 28.698 g, 0.623 g, 2.509g, 0.4 g are made into 200mL solution, as precipitating reagent, carry out co-precipitation with ammonium hydrogencarbonate under 60 ℃, controlling pH is 8-10, after completing, 1 h is stirred in continuation, then standing aging 16 h.The gained sediment is filtered, 90 ℃ of drying 12 h, 800 ℃ of roasting 5 h, obtain catalyst.

Embodiment 3:

Take respectively Ni (NO 3) 26H 2o, Al (NO 3) 39H 2o, Co (NO 3) 26H 2o, Zr (NO 3) 45H 2o and dispersing agent C 4.011 g, 30.464 g, 0.446 g, 0.836g, 0.5 g are made into 200 mL solution, as precipitating reagent, carry out co-precipitation with sodium carbonate under 80 ℃, controlling pH is 8-10, after completing, 1 h is stirred in continuation, then standing aging 16 h.The gained sediment is filtered, 90 ℃ of drying 12 h, 800 ℃ of roasting 6 h, obtain catalyst.

X-ray diffractogram after Fig. 1 catalyst (b) reduction that to be the catalyst (a) that obtains of the embodiment of the present invention 2 obtain with comparative example 1.As seen from Figure 1, the catalyst of the present invention design, add auxiliary agent, new diffraction maximum do not occur, and the disperse that becomes of each diffraction maximum peak shape, promoted the dispersion of each component, and the crystallite dimension of carrier and active component obviously reduces.

The graph of pore diameter distribution that Fig. 2 is the catalyst that obtains of various embodiments of the present invention.As seen from Figure 2, the catalyst of the present invention's design has the concentrated characteristics of pore-size distribution, and the most probable aperture is about 9 nm.

Fig. 3 be the catalyst that obtains of the embodiment of the present invention 3 after hydrothermal treatment consists, the CO methanation activity evaluation result at the differential responses temperature.Therefrom can find out that sample is after 800 ℃ of hydrothermal treatment consists 10 h, at 40000 mLh -1g -1high-quality air speed condition under, still there is higher activity, in the time of 340 ℃, the CO conversion ratio is greater than 90 %, obviously is better than the performance of the catalyst that document [Ind. Eng. Chem. Res. 2012,51,10352] reports.The catalyst that the present invention's design is described has excellent hydrothermal stability.

The transmission electron microscope picture that Fig. 4 is the catalyst that obtains of the embodiment of the present invention 3, the catalyst particle size of the present invention's design is little as seen from the figure, and the reactive metal size is 3-7 nm approximately, and it is more even to distribute.

The comparative example 1:

Take respectively Ni (NO 3) 26H 2o, Al (NO 3) 39H 2o and dispersing agent C 5.351 g, 37.528 g, 0.5 g are made into 200 mL solution, with sodium carbonate, as precipitating reagent, carry out co-precipitation under 80 ℃, and controlling pH is 8-10, and after completing, 1 h is stirred in continuation, then standing aging 16 h.The gained sediment is filtered, 90 ℃ of drying 12 h, 800 ℃ of roasting 6 h, obtain catalyst.

Catalytic performance test:

The Raney nickel fragmentation prepared in above-described embodiment and Comparative Examples is screened into 40-60 order particles, carries out catalytic performance test in the normal pressure continuous fixed bed reactor.The activity of catalyst means with the conversion ratio of carbon monoxide.Before reaction, 100 mg catalyst are mixed with 500 mg quartz sands, be loaded into the bottom of straight type quartz reactor, at 36.5 mL H 2/ 13.5 mL N 2after 1.5 h are processed in 750 ℃ of prereduction, make N in atmosphere 2purging is down to reaction temperature, then switches to reaction atmosphere: H 2volume fraction is 67.1 %, and the CO volume fraction is 22.4 %, and all the other are N 2, the catalyst quality air speed is 40000 mLh -1g -1.Gaseous product, by two gas-chromatographies (Shimadzu GC-2014C) on-line analysis, is analyzed H with the TCD detector 2, CO, CO 2and N 2, with FID, detect CH in product 4with a small amount of C 2h 4, C 2h 6.N 2be used for calculating the carbon monoxide conversion ratio as internal standard compound matter.

The active testing result of the catalyst prepared in above-described embodiment and Comparative Examples is as shown in the table:

Annotate:

Wherein, the volume flow that v is corresponding component.

In the methanation reaction of catalyst under high-speed, each probe temperature of interpolation auxiliary agent, the conversion ratio of carbon monoxide all is greater than 90 %, particularly in the time of 300 ℃ on initial activity apparently higher than the Comparative Examples of not adding auxiliary agent, therefore, the catalyst of the present invention's design has significant low-temperature catalytic activity.

Embodiment 3 is carried out to the hydrothermal stability test with Comparative Examples.By the sample of 750 ℃ of lower prereduction 1.5 h as for 800 ℃ of lower hydrothermal treatment consists 10 h (H 2o(g)/H 2=2, air speed 12000 mLh -1g -1).Get 100 mg and mix with 500 mg quartz sands through the catalyst of hydrothermal treatment consists, be loaded into the bottom of straight type quartz reactor, at 36.5 mL H 2/ 13.5 mL N 2after 0.5 h is processed in 750 ℃ of prereduction, make N in atmosphere 2purging is down to reaction temperature, then switches to reaction atmosphere: H 2volume fraction is 67.1 %, and the CO volume fraction is 22.4 %, and all the other are N 2, the reaction warm area is 300-450 ℃, mass space velocity is 40000 mLh -1g -1.Gaseous product is by two gas-chromatographies (Shimadzu GC-2014C) on-line analysis.

X-ray powder diffraction is analyzed on X ' the pert Pro diffractometer of Dutch Panalytic company and is carried out, and adopts X ' Celerator detector, Co-K α (λ=0.1789 nm) target emanation, and pipe is pressed 40 kV, pipe stream 40 mA, scanning step is 0.0167 o, every step 10 s, sweep limits is 2 θ=20-100 o.Size according to Scherrer formula estimation nickel crystallite.

The size (nm of unit) of nickel crystallite is as shown in the table after the catalyst reduction that above-described embodiment and Comparative Examples obtain and after hydrothermal treatment consists:

After carrying out hydrothermal treatment consists, nickel crystallite size increase amplitude is different, Comparatively speaking, adds auxiliary agent and can effectively suppress growing up of nickel crystallite.

Conclusion: the catalyst of the present invention's design has obvious advantage at aspects such as catalytic performance, hydrothermal stability and preparation technologies, is being rich in CO and H 2the methanation process process of gaseous mixture in have a good application prospect.

The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.

Claims (7)

1. a methanation of carbon monoxide catalyst, it is characterized in that: described catalyst is with Al 2o 3for carrier, Ni is active component, improves catalytic activity and the hydrothermal stability of catalyst by adding Zr and transition metal;
The percentage by weight of finished catalyst consists of:
Nickel 12-18 %
Transition metal 0-5 %
Zirconia 0-20 %
Aluminium oxide 65-88 %
The mass percent sum of each component is 100%.
2. the methanation of carbon monoxide catalyst according to claim 1, it is characterized in that: described transition metal is one or both in Fe, Co, Mn.
3. the methanation of carbon monoxide catalyst according to claim 1, it is characterized in that: the specific area of described catalyst is 150-200 m 2/ g, pore volume is 0.35-0.45 cm 3/ g, average pore size is 9.2-11.2 nm.
4. a method for preparing the methanation of carbon monoxide catalyst as claimed in claim 1 is characterized in that: comprise the following steps:
(1) by the soluble-salt of nickel, aluminium, zirconium and transition metal and dispersant wiring solution-forming, with alkali lye, as precipitating reagent, at 40-80 ℃, pH value, be to carry out neutralization precipitation under 8-10, aging 6-24 h then;
(2) sediment to pH<7, in 80-110 ℃ of dry 6-12 h, then, through 350-950 ℃ of roasting 1-6 h, makes described the methanation of carbon monoxide catalyst by the deionized water filtering and washing.
5. the preparation method of the methanation of carbon monoxide catalyst according to claim 4, it is characterized in that: the described soluble-salt of step (1) is sulfate, nitrate, acetate or chlorate.
6. the preparation method of the methanation of carbon monoxide catalyst according to claim 4 is characterized in that: the described dispersant of step (1) is a kind of in polyethylene glycol, polyacrylic acid, APEO, Arabic gum, laurate.
7. the preparation method of the methanation of carbon monoxide catalyst according to claim 4, it is characterized in that: the described precipitating reagent of step (1) is one or more in NaOH, potassium hydroxide, sodium carbonate, potash, ammonium carbonate, carbonic hydroammonium, ammoniacal liquor.
CN201310454106.4A 2013-09-29 2013-09-29 Carbon monoxide methanating catalyst and preparation method thereof CN103480375A (en)

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Cited By (11)

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CN105435802A (en) * 2015-11-25 2016-03-30 天津大学 Nanometer metal Ni-based catalyst as well as preparation method and application thereof
CN105498781A (en) * 2015-12-10 2016-04-20 大唐国际化工技术研究院有限公司 Coke-oven gas methanation catalyst and preparation method and application thereof
CN105727969A (en) * 2014-12-06 2016-07-06 中国石油化工股份有限公司 Preparation method of catalyst for synthetic gas methanation
CN105964268A (en) * 2016-05-17 2016-09-28 深圳市河科科技有限公司 Metal catalyst preparation method and preparation method of carbon nanotube
CN106622256A (en) * 2016-11-11 2017-05-10 中国五环工程有限公司 Preparation method of high-concentration CO methanation catalyst
CN106881106A (en) * 2017-04-14 2017-06-23 西南化工研究设计院有限公司 One kind conveying bed methanation catalyst and preparation method thereof
CN107224975A (en) * 2016-03-24 2017-10-03 中国石油化工股份有限公司 Preparation method without the methanation of carbon monoxide catalyst of reduction activation
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
WO2018141649A1 (en) 2017-01-31 2018-08-09 Clariant Produkte (Deutschland) Gmbh Manganese-doped nickel-methanation catalysts
CN108686661A (en) * 2017-04-06 2018-10-23 中国石油化工股份有限公司 A kind of preparation method of the methanation of carbon monoxide catalyst

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Cited By (15)

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CN105727969B (en) * 2014-12-06 2018-02-09 中国石油化工股份有限公司 A kind of preparation method of synthesis gas methanation catalyst
CN105727969A (en) * 2014-12-06 2016-07-06 中国石油化工股份有限公司 Preparation method of catalyst for synthetic gas methanation
CN105435802B (en) * 2015-11-25 2018-04-17 天津大学 A kind of Ni-based catalyst of nano metal and preparation method and application
CN105435802A (en) * 2015-11-25 2016-03-30 天津大学 Nanometer metal Ni-based catalyst as well as preparation method and application thereof
CN105498781A (en) * 2015-12-10 2016-04-20 大唐国际化工技术研究院有限公司 Coke-oven gas methanation catalyst and preparation method and application thereof
CN107224975A (en) * 2016-03-24 2017-10-03 中国石油化工股份有限公司 Preparation method without the methanation of carbon monoxide catalyst of reduction activation
CN105964268A (en) * 2016-05-17 2016-09-28 深圳市河科科技有限公司 Metal catalyst preparation method and preparation method of carbon nanotube
CN106622256A (en) * 2016-11-11 2017-05-10 中国五环工程有限公司 Preparation method of high-concentration CO methanation catalyst
CN106622256B (en) * 2016-11-11 2019-06-18 中国五环工程有限公司 A kind of preparation method of high concentration CO methanation catalyst
WO2018141649A1 (en) 2017-01-31 2018-08-09 Clariant Produkte (Deutschland) Gmbh Manganese-doped nickel-methanation catalysts
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
CN108686661A (en) * 2017-04-06 2018-10-23 中国石油化工股份有限公司 A kind of preparation method of the methanation of carbon monoxide catalyst
CN106881106A (en) * 2017-04-14 2017-06-23 西南化工研究设计院有限公司 One kind conveying bed methanation catalyst and preparation method thereof
CN106881106B (en) * 2017-04-14 2019-08-23 西南化工研究设计院有限公司 A kind of conveying bed methanation catalyst and preparation method thereof

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