CN104028270A - Methanation catalyst and preparation method thereof - Google Patents
Methanation catalyst and preparation method thereof Download PDFInfo
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- CN104028270A CN104028270A CN201410256862.0A CN201410256862A CN104028270A CN 104028270 A CN104028270 A CN 104028270A CN 201410256862 A CN201410256862 A CN 201410256862A CN 104028270 A CN104028270 A CN 104028270A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000012684 catalyst carrier precursor Substances 0.000 claims abstract description 14
- 239000000446 fuel Substances 0.000 claims abstract description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 54
- 239000008367 deionised water Substances 0.000 claims description 36
- 230000000694 effects Effects 0.000 claims description 30
- 238000002485 combustion reaction Methods 0.000 claims description 22
- 239000010453 quartz Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 19
- 239000012752 auxiliary agent Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 3
- 230000000996 additive effect Effects 0.000 abstract 3
- 238000001035 drying Methods 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 239000003245 coal Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 4
- 150000002169 ethanolamines Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 229910052622 kaolinite Inorganic materials 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000009841 combustion method Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a methanation catalyst. The methanation catalyst comprises the following components by weight percent: 5 to 60 percent of catalyst active component NiO and the balance of catalyst carrier Al2O3, and the methanation catalyst also can contain 1 to 25 percent by weight of additive M, wherein the additive M is selected from one or more of oxides of Ce, Ca, Co, La, Zr, Sm, Ba, Mn, Fe, Mo, Ti and Cu. The invention also provides a method for preparing the methanation catalyst. The method comprises the following steps: mixing a catalyst active component precursor, an additive M precursor and a catalyst carrier precursor according to the constituent ratio of the corresponding methanation catalyst, adding organic fuel to be uniformly mixed, and drying the mixture to form a gel product; burning the gel product, and washing and drying a reaction product to obtain the methanation catalyst. The methanation catalyst and the preparation method thereof are simple in operation and environment-friendly, have the advantages of low requirement on equipment, gradual changeability in manipulation, low cost, low energy consumption and the like and are particularly applicable to the industrialized mass production.
Description
Technical field
The present invention relates to preparation and the application thereof of catalyst, particularly a kind of methanation catalyst and preparation method thereof.
Background technology
China's energy resource structure is " many coals, few oil, has gas ", and petroleum resources is not enough, and coal resources are relatively abundant.Coal discharges a large amount of oxysulfides, nitrogen oxide and a large amount of dust in combustion process, can cause the weather such as acid rain, photochemical fog and pollute, and dust particularly PM2.5 can cause human respiratory disease.With respect to technology such as coal methyl alcohol processed, coal derived DME, DCL/Direct coal liquefaction, ICL for Indirect Coal Liquefaction, coal synthetic natural gas processed (SNG) has total efficiency of utilization high (more than 50%), unit calorific value cost of investment is low, and CO conversion ratio high (approaching 100%), used heat utilization rate high (attached product high temperature and high pressure steam), waste water are easily processed the advantage of (need not process and can be used as boiler feedwater or recirculated water).
In coal process for producing natural, Coal Gasification Technology is ripe, and key technology is methanation catalyst.Methanation catalyst generally consists of several parts such as catalytic active component, auxiliary agent, catalyst carriers.A kind of common method prepared by methanation catalyst is to contain the solution of aluminium source carrier presoma, nickel oxide precursor, auxiliary agent presoma, add precipitating reagent one step to be settled out catalyst precursors, then after filtration, the step such as washing, dry, roasting, moulding, prepare methanation catalyst.US Patent No. 3988262, US3988263 utilize respectively co-precipitation and precipitation from homogeneous solution technology, prepare nickel-alumina methanation catalyst.
Patent CN102513119A discloses a kind of preparation method of methanation catalyst, by the mixed solution K of aluminum nitrate, nickel nitrate, lanthanum nitrate
2cO
3carry out co-precipitation, having made aluminium oxide is carrier, and nickel is the methanation catalyst that main active component, lanthana are auxiliary agent.
In the process of traditional precipitation method Kaolinite Preparation of Catalyst, the precursor solution of carrier, active component, auxiliary agent need to be carried out to co-precipitation or fractional precipitation, after filtration, repeatedly washing, can remove unnecessary precipitating reagent impurity.In operating process, can produce a large amount of waste water, larger on the impact of environment.The problems such as meanwhile, the large-scale production for catalyst, exists complicated process of preparation, and the production cycle is longer, and energy consumption is large.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of methanation catalyst and preparation method thereof, support material comes from wherein a kind of of aluminum nitrate or boehmite or two kinds, main active component raw material comes from nickel nitrate, auxiliary agent active component comes from the Nitrates of some other metal, by solution combustion method, make methanation catalyst, preparation method has feature simply, easily and fast.
To achieve these goals, the technical solution used in the present invention is:
A methanation catalyst, its composition comprises: account for the catalyst activity component NiO of total catalyst weight 5～60% and the catalyst carrier Al of surplus
2o
3.
The present invention also provides a kind of method of preparing described methanation catalyst, comprises the following steps:
Step 1, mixes catalyst activity component precursor and catalyst carrier precursor according to the ratio of the composition of corresponding methanation catalyst, add organic-fuel to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product;
Step 2, gel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 300～600 ℃, carry out combustion reaction 45～60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst making.
Described catalyst activity component precursor is nickel nitrate, and catalyst carrier precursor is aluminum nitrate or boehmite.Before mixing, catalyst carrier precursor is dissolved in to deionized water and makes solution.
Described organic-fuel is ethylene glycol, hydrazine hydrate or monoethanolamine.
The molal quantity sum of described catalyst activity component precursor, catalyst carrier precursor is 1:(1-10 with organic-fuel mol ratio).
The another kind of form of methanation catalyst of the present invention, its composition comprises: account for the catalyst activity component NiO of total catalyst weight 5～60%, account for 1～25% auxiliary agent M of total catalyst weight and the catalyst carrier Al of surplus
2o
3, wherein, described auxiliary agent M is selected from one or more in the oxide of metal Ce, Ca, Co, La, Zr, Sm, Ba, Mn, Fe, Mo, Ti and Cu.
The method of preparing this another kind form methanation catalyst, comprises the following steps:
Step 1, mixes catalyst activity component precursor, auxiliary agent M precursor, catalyst carrier precursor according to the ratio of the composition of corresponding methanation catalyst, add organic-fuel to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product;
Step 2, gel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 300～600 ℃, carry out combustion reaction 45～60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst making.
Auxiliary agent M precursor is the nitrate of metal in auxiliary agent M, and the molal quantity sum of catalyst activity component precursor, auxiliary agent M precursor, catalyst carrier precursor is 1:(1-10 with organic-fuel mol ratio).
Compared with prior art, the invention has the beneficial effects as follows:
(1) simple to operate with method Kaolinite Preparation of Catalyst of the present invention, save traditional infusion process, coprecipitation etc. in the middle of Kaolinite Preparation of Catalyst process as evaporate to dryness solution, remove the loaded down with trivial details steps such as precipitating reagent.
(2) the present invention, by using existing nickel nitrate, auxiliary agent Nitrates, aluminum nitrate, in conjunction with the feature of organic-fuel, obtains nano level metal oxide powder by combustion method.
(3) while preparing methanation catalyst by method of the present invention, do not produce waste water, environmentally friendly.
In a word, the present invention has that equipment requirement is low, technique is simple, handle gradual change, cost is low, low power consumption and other advantages, is particularly suitable for producing with large-scale industrialization.
The specific embodiment
Below in conjunction with embodiment, describe embodiments of the present invention in detail.
Embodiment 1
The preparation method of the present embodiment comprises the following steps:
Step 1, take 294.3 grams of Al (NO
3)
39H
2o, 77.6 grams of Ni (NO
3)
26H
2o is dissolved in a small amount of deionized water, adds 310 grams of ethylene glycol to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product.
Step 2, jel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 500 ℃, carry out combustion reaction 60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst 20%NiO/ γ-Al making
2o
3(ethylene glycol A).
Composition and the activity rating of catalyst the results are shown in Table 1.
Embodiment 2
The preparation method of the present embodiment comprises the following steps:
Step 1, take 294.3 grams of Al (NO
3)
39H
2o, 77.6 grams of Ni (NO
3)
26H
2o is dissolved in a small amount of deionized water, adds 305 grams of monoethanolamines to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product.
Step 2, jel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 500 ℃, carry out combustion reaction 60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst 20%NiO/ γ-Al making
2o
3(monoethanolamine A).
Composition and the activity rating of catalyst the results are shown in Table 1.
Embodiment 3
The preparation method of the present embodiment comprises the following steps:
Step 1, take 294.3 grams of Al (NO
3)
39H
2o, 77.6 grams of Ni (NO
3)
26H
2o is dissolved in a small amount of deionized water, adds 250 grams of hydrazine hydrates to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product.
Step 2, jel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 500 ℃, carry out combustion reaction 60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst 20%NiO/ γ-Al making
2o
3(hydrazine hydrate A).
Composition and the activity rating of catalyst the results are shown in Table 1.
Embodiment 4
The preparation method of the present embodiment comprises the following steps:
Step 1, take 102 grams of boehmites, 77.6 grams of Ni (NO
3)
26H
2o is dissolved in a small amount of deionized water, adds 250 grams of ethylene glycol to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product.
Step 2, jel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 500 ℃, carry out combustion reaction 60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst 20%NiO/ γ-Al making
2o
3(ethylene glycol B).
Composition and the activity rating of catalyst the results are shown in Table 1.
Embodiment 5
The preparation method of the present embodiment comprises the following steps:
Step 1, take 102 grams of boehmites, 77.6 grams of Ni (NO
3)
26H
2o is dissolved in a small amount of deionized water, adds 305 grams of monoethanolamines to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product.
Step 2, jel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 500 ℃, carry out combustion reaction 60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst 20%NiO/ γ-Al making
2o
3(monoethanolamine B).
Composition and the activity rating of catalyst the results are shown in Table 1.
Embodiment 6
The preparation method of the present embodiment comprises the following steps:
Step 1, take 102 grams of boehmites, 77.6 grams of Ni (NO
3)
26H
2o is dissolved in a small amount of deionized water, adds 250 grams of hydrazine hydrates to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product.
Step 2, jel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 500 ℃, carry out combustion reaction 60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst 20%NiO/ γ-Al making
2o
3(hydrazine hydrate B).
Composition and the activity rating of catalyst the results are shown in Table 1.
Embodiment 7
The preparation method of the present embodiment comprises the following steps:
Step 1, take 276 grams of Al (NO
3)
39H
2o, 77.6 grams of Ni (NO
3)
26H
2o, 32 grams of Mg (NO
3)
26H
2o is dissolved in a small amount of deionized water, adds 310 grams of ethylene glycol to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product.
Step 2, jel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 500 ℃, carry out combustion reaction 60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst 20%NiO5%MgO/ γ-Al making
2o
3(ethylene glycol A).
Composition and the activity rating of catalyst the results are shown in Table 1.
Embodiment 8
The preparation method of the present embodiment comprises the following steps:
Step 1, take 276 grams of Al (NO
3)
39H
2o, 77.6 grams of Ni (NO
3)
26H
2o, 13.3 grams of La (NO
3)
36H
2o is dissolved in a small amount of deionized water, adds 310 grams of ethylene glycol to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product.
Step 2, jel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 500 ℃, carry out combustion reaction 60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst 20%NiO5%La making
2o
3/ γ-Al
2o
3(ethylene glycol A).
Composition and the activity rating of catalyst the results are shown in Table 1.
Embodiment 9
The preparation method of the present embodiment comprises the following steps:
Step 1, take 276 grams of Al (NO
3)
39H
2o, 77.6 grams of Ni (NO
3)
26H
2o, 32 grams of Mg (NO
3)
26H
2o is dissolved in a small amount of deionized water, adds 305 grams of monoethanolamines to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product.
Step 2, jel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 500 ℃, carry out combustion reaction 60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst 20%NiO5%MgO/ γ-Al making
2o
3(monoethanolamine A).
Composition and the activity rating of catalyst the results are shown in Table 1.
Embodiment 10
The preparation method of the present embodiment comprises the following steps:
Step 1, take 276 grams of Al (NO
3)
39H
2o, 77.6 grams of Ni (NO
3)
26H
2o, 13.3 grams of La (NO
3)
36H
2o is dissolved in a small amount of deionized water, adds 250 grams of hydrazine hydrates to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product.
Step 2, jel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 500 ℃, carry out combustion reaction 60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst 20%NiO5%La making
2o
3/ γ-Al
2o
3(hydrazine hydrate A).
Composition and the activity rating of catalyst the results are shown in Table 1.
Embodiment 11
The preparation method of the present embodiment comprises the following steps:
Step 1, take 96 grams of boehmites, 77.6 grams of Ni (NO
3)
26H
2o, 32 grams of Mg (NO
3)
26H
2o is dissolved in a small amount of deionized water, adds 310 grams of ethylene glycol to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product.
Step 2, jel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 500 ℃, carry out combustion reaction 60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst 20%NiO5%MgO/ γ-Al making
2o
3(ethylene glycol B).
Composition and the activity rating of catalyst the results are shown in Table 1.
Embodiment 12
The preparation method of the present embodiment comprises the following steps:
Step 1, take 96 grams of boehmites, 77.6 grams of Ni (NO
3)
26H
2o, 13.3 grams of La (NO
3)
36H
2o is dissolved in a small amount of deionized water, adds 310 grams of ethylene glycol to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product.
Step 2, jel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 500 ℃, carry out combustion reaction 60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst 20%NiO5%La making
2o
3/ γ-Al
2o
3(ethylene glycol B).
Composition and the activity rating of catalyst the results are shown in Table 1.
Embodiment 13
The preparation method of the present embodiment comprises the following steps:
Step 1, take 96 grams of boehmites, 77.6 grams of Ni (NO
3)
26H
2o, 13.3 grams of La (NO
3)
36H
2o is dissolved in a small amount of deionized water, adds 305 grams of monoethanolamines to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product.
Step 2, jel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 500 ℃, carry out combustion reaction 60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst 20%NiO5%La making
2o
3/ γ-Al
2o
3(monoethanolamine B).
Composition and the activity rating of catalyst the results are shown in Table 1.
Embodiment 14
The preparation method of the present embodiment comprises the following steps:
Step 1, take 276 grams of Al (NO
3)
39H
2o, 97 grams of Ni (NO
3)
26H
2o is dissolved in a small amount of deionized water, adds 310 grams of ethylene glycol to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product.
Step 2, jel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 500 ℃, carry out combustion reaction 60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst 25%NiO/ γ-Al making
2o
3(ethylene glycol A).
Composition and the activity rating of catalyst the results are shown in Table 1.
Embodiment 15
The preparation method of the present embodiment comprises the following steps:
Step 1, take 257.6 grams of Al (NO
3)
39H
2o, 97 grams of Ni (NO
3)
26H
2o, 13.8 grams of Zr (NO
3)
43H
2o is dissolved in a small amount of deionized water, adds 310 grams of ethylene glycol to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product.
Step 2, jel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 500 ℃, carry out combustion reaction 60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst 25%NiO5%ZrO making
2/ γ-Al
2o
3(ethylene glycol A).
Composition and the activity rating of catalyst the results are shown in Table 1.
The catalytic activity of the above embodiment of the present invention gained methanation catalyst is measured, and in fixed bed reactors, carries out.Get 40～60 object catalyst granules and pack in reactor, logical people's hydrogen then reduces 4h at the temperature of 550 ℃, is the catalyst of reduction activation.After reduction finishes, the temperature stabilization of beds, under the reaction temperature of appointment, is switched to H
2/ CO ratio be 3.07 synthesis gas as unstripped gas, under condition of normal pressure, carry out methanation reaction.The composition of unstripped gas and reactor outlet gas is all by gas chromatograph on-line analysis, by calculating the selective of the conversion ratio of methanation reaction and product.
By embodiment, illustrate, according to method of the present invention, through parameters such as regulation and control raw material ratio, dispersant, incendiary agent, combustion reaction temperature, combustion reaction times, can one-step synthesis go out methanation catalyst.And methanation catalyst provided by the invention has the advantages such as catalytic activity is good, preparation technology is simple, with low cost, is a kind of synthesis gas methanation catalyst that has very much actual application prospect.
The methanation catalytically active assessment result of each embodiment catalyst of table 1
Claims (10)
1. a methanation catalyst, its composition comprises: account for the catalyst activity component NiO of total catalyst weight 5～60% and the catalyst carrier Al of surplus
2o
3.
2. a method of preparing methanation catalyst described in claim 1, is characterized in that, comprises the following steps:
Step 1, mixes catalyst activity component precursor and catalyst carrier precursor according to the ratio of the composition of corresponding methanation catalyst, add organic-fuel to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product;
Step 2, gel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 300～600 ℃, carry out combustion reaction 45～60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst making.
3. prepare according to claim 2 the method for methanation catalyst, it is characterized in that, described catalyst activity component precursor is nickel nitrate, and catalyst carrier precursor is aluminum nitrate or boehmite.
4. prepare according to claim 3 the method for methanation catalyst, it is characterized in that, before mixing, catalyst carrier precursor is dissolved in to deionized water and makes solution.
5. prepare according to claim 2 the method for methanation catalyst, it is characterized in that, described organic-fuel is ethylene glycol, hydrazine hydrate or monoethanolamine.
6. according to the method for preparing methanation catalyst described in claim 2 or 3 or 4 or 5, it is characterized in that, the molal quantity sum of described catalyst activity component precursor, catalyst carrier precursor is 1:(1-10 with organic-fuel mol ratio).
7. a methanation catalyst, its composition comprises: account for the catalyst activity component NiO of total catalyst weight 5～60%, account for 1～25% auxiliary agent M of total catalyst weight and the catalyst carrier Al of surplus
2o
3, wherein, described auxiliary agent M is selected from one or more in the oxide of metal Ce, Ca, Co, La, Zr, Sm, Ba, Mn, Fe, Mo, Ti and Cu.
8. a method of preparing methanation catalyst described in claim 7, is characterized in that, comprises the following steps:
Step 1, mixes catalyst activity component precursor, auxiliary agent M precursor, catalyst carrier precursor according to the ratio of the composition of corresponding methanation catalyst, add organic-fuel to mix, and under 80 ℃ of conditions, dry 5h is to forming gel product;
Step 2, gel product is transferred in crucible or quartz boat, directly put into the constant temperature Muffle furnace that is redefined for 300～600 ℃, carry out combustion reaction 45～60 minutes, take out solid matter after burning use washed with de-ionized water, dry after, be the catalyst making.
9. prepare according to claim 8 the method for methanation catalyst, it is characterized in that, described catalyst activity component precursor is nickel nitrate, and auxiliary agent M precursor is the nitrate of metal in auxiliary agent M, and catalyst carrier precursor is aluminum nitrate or boehmite.
10. prepare according to claim 8 or claim 9 the method for methanation catalyst, it is characterized in that, the molal quantity sum of described catalyst activity component precursor, auxiliary agent M precursor, catalyst carrier precursor is 1:(1-10 with organic-fuel mol ratio).
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