CN105032443A - Methanation catalyst - Google Patents
Methanation catalyst Download PDFInfo
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- CN105032443A CN105032443A CN201510230574.2A CN201510230574A CN105032443A CN 105032443 A CN105032443 A CN 105032443A CN 201510230574 A CN201510230574 A CN 201510230574A CN 105032443 A CN105032443 A CN 105032443A
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Abstract
The invention discloses a methanation catalyst which is prepared through following processes: (1) weighing ammonium metatungstate and nickel nitrate and placing the raw materials in deionized water with stirring, and adding phosphoric acid until the raw materials are completely dissolved and adding deionized water to a certain volume to form a co-impregnation liquid; (2) under a nitrogen atmosphere, crushing 58 wt% hematite into powdery particles being less than 100 [mu]m in size and dissolving the particles with an HCl solution in deionized water, and intensively stirring the solution under the nitrogen atmosphere; (3) adding the solution dropwisely to a NaOH solution, separating-out a precipitation, washing the precipitation in deionized water for four times, drying the product in a drying oven at 80 DEG C, adding the co-impregnation liquid and stirring the solution to fully mix the mixture; and (4) vacuum-drying the mixture and calcining the mixture in a tube furnace under a nitrogen atmosphere to prepare the catalyst. The methanation catalyst is prepared through the novel method, is good in anti-carbon-deposition capability, is excellent in activity and is low in preparation cost.
Description
Technical field
The present invention relates to a kind of methanation catalyst, belong to catalyst field.
Background technology
China's coke output in 2009 3.53 hundred million tons, wherein 1/3 production capacity is in integrated iron and steel works, and 2/3 at independently coal chemical enterprise.400m is about by coke by-product per ton
3oven gas calculates, independent enterprise annual by-product coke furnace gas 1,412 hundred million m
3left and right, heat except personal and civilian (making town gas), production synthetic ammonia or methyl alcohol except melting down, the oven gas diffused every year is more than 20,000,000,000 m
3, " the amount of West-east Gas first stage of the project natural gas that calorific value exceedes.At present, China's oven gas is mainly used in hydrogen manufacturing, synthesizing methanol and synthetic ammonia.From the composition of oven gas, the many carbon of hydrogen is few, and synthesizing methanol is not most economical utilization ways; And from the contrast of capacity usage ratio, compressed natural gas (CNG) is produced again further by methanation production synthetic natural gas (SNG) with oven gas, its capacity usage ratio can reach more than 80%, and the capacity usage ratio of preparing methanol from coke oven gas is only 52% ~ 59%.The current market of methyl alcohol are low on the other hand, and profit is limited, complex process, invests high, and employing coke-oven gas for production of methane synthesis SNG produces CNG more further, and its flow process is relatively simple, investment is lower, good in economic efficiency, have very strong competitiveness.Along with crude oil price constantly goes up, gas price is also constantly rising violently, and CNG is as alternative motor fuels, its cost ratio gasoline is much lower, therefore has very large attraction, especially in the field such as taxi and bus, current methanation catalyst carbon distribution is higher, active low.
Summary of the invention
For above-mentioned prior art Problems existing, the invention provides a kind of methanation catalyst, carbon accumulation resisting ability is higher.
To achieve these goals, the technical solution used in the present invention is: a kind of methanation catalyst, is characterized in that, the preparation method of described catalyst is:
Take 85g ammonium metatungstate and 40g nickel nitrate is placed in 120ml deionized water, stir, until completely dissolved, then add 8ml phosphoric acid, then add deionized water constant volume to 200ml, make co-impregnated solution;
Under N2 atmosphere, 58wt% ground hematite is broken into the powdered granule being less than 100 μm, and and the HCl solubilize of 1L12mol/L in 8L deionized water, vigorous stirring under N2 atmosphere, by in the NaOH solution of above-mentioned dropwise instillation 250mL0.5mol/L, after reaction terminates, sediment is separated, washs above-mentioned precipitation four times by 200mL deionized water, then product is dry in 80 DEG C of baking ovens, cooling
Add above-mentioned co-impregnated solution, stir and make it fully mix, and ultrasonic, the standing 4h of difference, sediment is in 90 DEG C of vacuum drying 10h, and finally 600-800 DEG C of calcining in N2 atmosphere tube type stove, obtains catalyst.
Further improvement, the temperature that sediment is calcined in N2 atmosphere tube type stove is 760 DEG C.
Further improvement, described sediment calcination time in N2 atmosphere tube type stove is 3h.
Of the present inventionly prepare methanation catalyst by new preparation method, draw to have good carbon accumulation resisting ability by experiment, and have good activity, preparation cost is comparatively cheap.
Detailed description of the invention
The invention will be further described below.
Embodiment:
Take 85g ammonium metatungstate and 40g titanium sulfate is placed in 120ml deionized water, stir, until completely dissolved, then add 8ml phosphoric acid, then add deionized water constant volume to 200ml, make co-impregnated solution;
Under N2 atmosphere, 58wt% ground hematite is broken into the powdered granule being less than 100 μm, and and the HCl solubilize of 1L12mol/L in 8L deionized water, vigorous stirring under N2 atmosphere, by the NaOH solution of above-mentioned dropwise instillation 250mL0.5mol/L, after reaction terminates, sediment is separated, washs above-mentioned precipitation four times by 200mL deionized water, then that product is dry in 80 DEG C of baking ovens, cooling
Add above-mentioned co-impregnated solution, stir and make it fully mix, and ultrasonic, the standing 4h of difference, sediment is in 90 DEG C of vacuum drying 10h, and finally 760 DEG C of calcining 3h in N2 atmosphere tube type stove, obtain catalyst.
Comparative example 1:
Take 85g ammonium metatungstate and 40g titanium sulfate is placed in 120ml deionized water, stir, until completely dissolved, then add 8ml phosphoric acid, then add deionized water constant volume to 200ml, make co-impregnated solution;
58wt% ground hematite is broken into the powdered granule being less than 100 μm, and and the HCl solubilize of 1L12mol/L in 8L deionized water, vigorous stirring, by in the NaOH solution of above-mentioned dropwise instillation 250mL0.5mol/L, after reaction terminates, sediment is separated, above-mentioned precipitation is washed four times by 200mL deionized water, then product is dry in 80 DEG C of baking ovens, cooling, add above-mentioned co-impregnated solution, stirring makes it fully mix, and it is ultrasonic respectively, leave standstill 4h, sediment is in 90 DEG C of vacuum drying 10h, finally 500 DEG C of calcining 2h in tube furnace, obtain catalyst.
Comparative example 2:
Take 85g ammonium metatungstate and 40g nickel nitrate is placed in 120ml deionized water, stir, until completely dissolved, then add 8ml phosphoric acid, then add deionized water constant volume to 200ml, make co-impregnated solution;
58wt% ground hematite is broken into the powdered granule being less than 100 μm, and and the HCl solubilize of 1L12mol/L in 8L deionized water, vigorous stirring, by in the NaOH solution of above-mentioned dropwise instillation 250mL0.5mol/L, after reaction terminates, sediment is separated, above-mentioned precipitation is washed four times by 200mL deionized water, then that product is dry in 80 DEG C of baking ovens, cooling, add above-mentioned co-impregnated solution, stirring makes it fully mix, and ultrasonic, the standing 4h of difference, sediment is in 90 DEG C of vacuum drying 10h, in tube furnace, 600 DEG C of calcining 4h, obtain catalyst.
Comparative example 3
Take 85g ammonium metatungstate and 40g copper sulphate is placed in 120ml deionized water, stir, until completely dissolved, then add 8ml phosphoric acid, then add deionized water constant volume to 200ml, make co-impregnated solution;
Under N2 atmosphere, 58wt% ground hematite is broken into the powdered granule being less than 100 μm, and and the HCl solubilize of 1L12mol/L in 8L deionized water, vigorous stirring under N2 atmosphere, by the NaOH solution of above-mentioned dropwise instillation 250mL0.5mol/L, after reaction terminates, sediment is separated, washs above-mentioned precipitation four times by 200mL deionized water, then that product is dry in 80 DEG C of baking ovens, cooling
Add above-mentioned co-impregnated solution, stir and make it fully mix, and ultrasonic, the standing 4h of difference, sediment is in 90 DEG C of vacuum drying 10h, and finally 560 DEG C of calcining 3h in N2 atmosphere tube type stove, obtain catalyst
Methanation catalyst carbon accumulation resisting ability evaluation method:
Adopt φ 38 × 3.5mm stainless steel single tube reactor.Catalyst test sample 1.70mm aperture testing sieve is screened out powder, rejects half, then weigh with the complete granularity sample of the tightly packed 100mL of 250mL graduated cylinder, try to achieve bulk density, then take the sample being equivalent to 30mL quality for subsequent use.
By the granularity handled well for (2 ~ 3) mm quartz sand loads in reactor, knock jolt ramming gently, be filled to the height determined when measuring isothermal region, add one deck alloy network, pour the catalyst samples jolt ramming got ready into, add one deck alloy network again, finally reinstall quartz sand to thermocouple sheath top end, tighten reactor end head nut.
By the reactor access test device systematic filled, shutdown system all outlet ports valve and atmospheric valve, pass into pure hydrogen, makes system boost to 6.0MPa, and stop ventilation, in 5min, its pressure does not fall.Otherwise the inspection of application expanding foam solution, processes air-leak section, can carry out lower step test after leak test is qualified.
Catalyst is at normal pressure, air speed 10000h
-1, 500 DEG C of reduction 6h, reducing gases is pure hydrogen.
After reduction terminates, switch source of the gas, pass into reactor feed gas, and in 1h, reaction pressure is risen to 3.0MPa, temperature is risen to 650 DEG C as early as possible, reacts 240h at this temperature.Then cut off source of the gas, Pressure Drop is to normal pressure, Temperature fall to room temperature.Carefully draw off catalyst, adopt x-ray photoelectron power spectrum (XPS) quantitative analysis catalyst surface carbon element content (atomic percent).According to the height of catalyst surface carbon element content, characterize catalyst carbon accumulation resisting ability strong and weak.
Catalyst carbon accumulation resisting ability experimental condition:
Catalyst loading amount 30mL
The former granularity of catalyst grain size
Pressure 3.0MPa
Temperature 650 DEG C
Air speed 10000h
-1
Time 240h
Unstripped gas composition H
240%CO25%CO
25%CH
410%H
2o20% (all with volume fraction)
Methanation catalyst activity rating method:
Adopt φ 38 × 3.5mm stainless steel single tube reactor.Catalyst test sample 1.70mm aperture testing sieve is screened out powder, rejects half, then weigh with the complete granularity sample of the tightly packed 100mL of 250mL graduated cylinder, try to achieve bulk density, then take the sample being equivalent to 30mL quality for subsequent use.
By the granularity handled well for (2 ~ 3) mm quartz sand loads in reactor, knock jolt ramming gently, be filled to the height determined when measuring isothermal region, add one deck alloy network, pour the catalyst samples jolt ramming got ready into, add one deck alloy network again, finally reinstall quartz sand to thermocouple sheath top end, tighten reactor end head nut.
By the reactor access test device systematic filled, shutdown system all outlet ports valve and atmospheric valve, pass into pure hydrogen, makes system boost to 6.0MPa, and stop ventilation, in 5min, its pressure does not fall.Otherwise the inspection of application expanding foam solution, processes air-leak section, can carry out lower step test after leak test is qualified.
Catalyst is at normal pressure, air speed 10000h
-1, 500 DEG C of reduction 6h, reducing gases is pure hydrogen.
After reduction terminates, temperature is risen to 650 DEG C as early as possible, at this temperature heat-resisting 10h.After heat-resisting end, be cooled to 300 DEG C, switch source of the gas, pass into reactor feed gas, and in 1h, reaction pressure is risen to 3.0MPa, after stablizing 2h by catalyst activity appreciation condition, start analysis reactor outlet CO gas volume fraction.Activity represents with CO conversion.
Computing formula is: (Reactor inlet CO gas volume fraction-reactor outlet CO gas volume fraction) is divided by Reactor inlet CO gas volume fraction
Catalyst activity appreciation condition:
Catalyst loading amount 30mL
The former granularity of catalyst grain size
Activity determination pressure 3.0MPa
Activity determination temperature 300 DEG C
Heat resisting temperature 700 DEG C
Heat-resistant time 10h
Activity determination air speed 10000h
-1
Unstripped gas composition H
240%CO25%CO
25%CH
410%H
2o20% (all with volume fraction)
| Catalyst | Carbon accumulation resisting ability (surface carbon atomic ratio) | Active (co conversion ratio) |
| Embodiment | 0.1 | 97 |
| Comparative example 1 | 5.2 | 74 |
| Comparative example 2 | 7.8 | 77 |
| Comparative example 3 | 8.9 | 72 |
Claims (3)
1. a methanation catalyst, is characterized in that, the preparation method of described catalyst is:
Take 85g ammonium metatungstate and 40g nickel nitrate is placed in 120ml deionized water, stir, until completely dissolved, then add 8ml phosphoric acid, then add deionized water constant volume to 200ml, make co-impregnated solution;
Under N2 atmosphere, 58wt% ground hematite is broken into the powdered granule being less than 100 μm, and and the HCl solubilize of 1L12mol/L in 8L deionized water, vigorous stirring under N2 atmosphere, by in the NaOH solution of above-mentioned dropwise instillation 250mL0.5mol/L, after reaction terminates, sediment is separated, washs above-mentioned precipitation four times by 200mL deionized water, then product is dry in 80 DEG C of baking ovens, cooling
Add above-mentioned co-impregnated solution, stir and make it fully mix, and ultrasonic, the standing 4h of difference, sediment is in 90 DEG C of vacuum drying 10h, and finally 600-800 DEG C of calcining in N2 atmosphere tube type stove, obtains catalyst.
2. a kind of methanation catalyst according to claim 1, it is characterized in that, the temperature that sediment is calcined in N2 atmosphere tube type stove is 760 DEG C.
3. a kind of methanation catalyst according to claim 2, is characterized in that described sediment calcination time in N2 atmosphere tube type stove is 3h.
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| CN201510230574.2A CN105032443A (en) | 2015-05-08 | 2015-05-08 | Methanation catalyst |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS529692A (en) * | 1975-07-14 | 1977-01-25 | Showa Denko Kk | Catalyst for removing nox in exhaust gas |
| CN102247850A (en) * | 2011-05-26 | 2011-11-23 | 肖天存 | Methanation catalyst, preparation process thereof and methanation reaction device |
| CN103203237A (en) * | 2013-05-02 | 2013-07-17 | 神华集团有限责任公司 | Aluminum oxide loaded methanation catalyst |
| CN103433042A (en) * | 2013-08-26 | 2013-12-11 | 河南理工大学 | Red mud supported nickel catalyst used for ammonia decomposition for hydrogen production and preparation method thereof |
| CN104399466A (en) * | 2014-11-13 | 2015-03-11 | 大连理工大学 | Iron-containing natural ore loaded nickel methanation catalyst and preparation method thereof |
-
2015
- 2015-05-08 CN CN201510230574.2A patent/CN105032443A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS529692A (en) * | 1975-07-14 | 1977-01-25 | Showa Denko Kk | Catalyst for removing nox in exhaust gas |
| CN102247850A (en) * | 2011-05-26 | 2011-11-23 | 肖天存 | Methanation catalyst, preparation process thereof and methanation reaction device |
| CN103203237A (en) * | 2013-05-02 | 2013-07-17 | 神华集团有限责任公司 | Aluminum oxide loaded methanation catalyst |
| CN103433042A (en) * | 2013-08-26 | 2013-12-11 | 河南理工大学 | Red mud supported nickel catalyst used for ammonia decomposition for hydrogen production and preparation method thereof |
| CN104399466A (en) * | 2014-11-13 | 2015-03-11 | 大连理工大学 | Iron-containing natural ore loaded nickel methanation catalyst and preparation method thereof |
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Application publication date: 20151111 |