CN102614887A - Catalytic agent and preparation method for preparing natural gas by mixing coke-oven gas and straw gas - Google Patents
Catalytic agent and preparation method for preparing natural gas by mixing coke-oven gas and straw gas Download PDFInfo
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- CN102614887A CN102614887A CN2012100457465A CN201210045746A CN102614887A CN 102614887 A CN102614887 A CN 102614887A CN 2012100457465 A CN2012100457465 A CN 2012100457465A CN 201210045746 A CN201210045746 A CN 201210045746A CN 102614887 A CN102614887 A CN 102614887A
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Abstract
The invention belongs to the technical field of methanation catalytic agents, particularly relates to a methanation catalytic agent and a preparation method for preparing natural gas by mixing coke-oven gas and straw gas in a natural gas synthetic process. The catalytic agent comprises a carrier, an active component and an accessory ingredient, the carrier is AI2O3 and MgO, the active component is NiO, the accessory ingredient is La2O3, and the catalytic agent comprises, by weight, 30-50% of NiO, 1-5% of La2O3, 30-50% of AI2O3, 12-20% of MgO and 1-3% of graphite. The preparation method of the catalytic agent comprises depositing and reacting to prepare semi-finished products, drying, burning, mixing materials, compressing and molding. The catalytic agent has the advantages of being good in activity, heat stability and carbon resisting performance, having good thermostability and the like.
Description
Technical field
The invention belongs to the methanation catalyst technical field, particularly a kind ofly be mixed with methanation catalyst and preparation method thereof in the synthetic natural gas process with oven gas and Straw Gas.
Background technology
Natural gas has efficiently, clean, transmit characteristic easily, be a kind of comparatively ideal clean energy resource, yet China is a rich coal, few oil, stingy country.For accelerating the problem of China's combustion gas imbalance between supply and demand; Except the existing resource of basing on our country; Also must be by all kinds of means, multimode enlarges resource provision; Satisfy the market demand that the order benefit increases, most of at present coal resources with China's abundant carry out gas methanation or the coke-oven gas methanation mode develops the manufactured gas, manufactured fuel gas, and gas supply is provided.But contain a large amount of hydrogen (seeing the following form) in the oven gas, a large amount of hydrogen-containing gas of meeting by-product when producing artificial natural gas, this hydrogen-containing gas reclaims or does combustion gas or further process hydrogen manufacturing with PSA.
Coke oven gas composition (F.V%)
Component H
2CH
4N
2O
2CO CO
2C
nH
m
Gas methanation has only large-scale production, and reclaiming a large amount of accessory substances just has economy.
China is large agricultural country, and annual all have a large amount of stalks, and stalk fuel not only efficient is low, and causes big pollution.The straight cracking of stalk high temperature is made Straw Gas (its component sees the following form), just mix with the coke oven gas phase and can between hydrocarbon and hydrogen, complementation carry out methanation, more reasonable economically.
Stalk gas composition (F.V%)
Component H
2CH
4N
2O
2CO CO
2C
nH
m
In the methanation catalyst technical field, be to be used for ammonia synthesizing industry the earliest, the synthetic ammonia methanation catalyst is used for the oxycarbide hydrogenation methanation reaction of low concentration, with the purified ammonia synthetic raw gas, this technical maturity.Because oxycarbide only accounts for gas 0.3 ~ 0.7%; And the methanation reaction liberated heat is few; And the mixed oxycarbide content of oven gas and Straw Gas is 10 ~ 30%, and its content is quite high, because the methanation reaction thermal discharge is big; The reaction adiabatic temperature rise is very big, Gu and the hear resistance of synthetic methane catalyst, high temperature resistant, stability are had higher requirement.At present, also not large-scale production of domestic coal preparing natural gas distinguished, and its methanation catalyst also is in the development stage.
Coke-oven gas methanation catalyst also has some patent reports; Like " a kind of coke-oven gas methanation catalyst and preparation method thereof " (patent No. ZL200810046429.9); This patent catalyst is used for coke-oven gas methanation; Its carrier magnesium aluminate spinel is to make with high-temperature calcination, and reactive metal is introduced with impregnation method.This its purposes of this catalyst, preparation method are different fully with methanation catalyst provided by the present invention.CN201110188574.2 also discloses a kind of catalyst that is used for coal preparing natural gas methanator, but this catalyst CO conversion ratio in methanation reaction is lower, is unfavorable for industrial applications.
Summary of the invention
Technical problem to be solved by this invention provides the Catalysts and its preparation method that a kind of oven gas and Straw Gas are mixed with natural gas.This catalyst has conversion ratio height, active good, is convenient to commercial Application and promotes.
The present invention solves the problems of the technologies described above the technical scheme that is adopted:
A kind of oven gas and Straw Gas are mixed with the catalyst of artificial natural gas, comprise carrier, active constituent and auxiliary agent, and said carrier is Al
2O
3, MgO, active component is NiO, auxiliary agent is La
2O
3, each component and mass percent thereof are in this catalyst: NiO 30 ~ 50%, La
2O
31 ~ 5%, Al
2O
330 ~ 50%, MgO 12 ~ 20%, graphite 1 ~ 3%.
H in the mixed gaseous mixture of said oven gas and Straw Gas
2Mol ratio 3.0 ~ 4.0:1.0 with CO.
A kind of oven gas and Straw Gas are mixed with the Preparation of catalysts method of artificial natural gas, comprise the steps:
(1) precipitation reaction makes the catalyst semi-finished product: placing response still in water bath with thermostatic control is the Ni (NO of 26.54 ~ 44.24g/L with concentration
3)
26H
2The O aqueous solution; 50.13 the Al (NO of ~ 83.50g/L
3)
39H
2The O aqueous solution; 17.35 the Mg (NO of ~ 28.92g/L
3)
26H
2La (the NO of the O aqueous solution and 0.60 ~ 3.02g/L
3)
36H
2The O aqueous solution adds in the agitated reactor, adds precipitating reagent K when under stirring condition, being heated to 65 ~ 75 ℃
2CO
3To K
2CO
3Mass percent concentration be 10 ~ 12%, in whole precipitation reaction process, keep 68 ~ 70 ℃, regulator solution pH value to 9.0 ~ 9.5; The resulting sediment of filtration washing is the catalyst semi-finished product;
(2) drying: with catalyst semi-finished product under 120 ~ 150 ℃ of conditions dry 4 ~ 5 hours;
(3) calcining: with dried catalyst semi-finished product 300 ~ 450 ℃ temperature lower calcination 3 ~ 4 hours;
(4) mix: the catalyst semi-finished product after will calcine and graphite are by grinding in mass ratio 100:1 ~ 3 adding ball mills and mixing, and its mixture is all through 200 mesh sieves;
(5) compression moulding: the distilled water of adding 6 ~ 12% mixes back compression moulding and promptly obtains the catalyst finished product.
Among this preparation method, the nickel nitrate of step (1), aluminum nitrate, magnesium nitrate, lanthanum nitrate is all chemical reagent, the Ni (NO of 26.54 ~ 44.24g/L
3)
26H
2O representes Ni (NO in every L solution
3)
26H
2The weight of O is 26.54 ~ 44.24g, Ni (NO
3)
26H
2O, Al (NO
3)
39H
2O, Mg (NO
3)
26H
2O, La (NO
3)
36H
2After nitrate such as O and the precipitating reagent generation precipitation reaction, the calcining back forms with NiO, La
2O
3, Al
2O
3, MgO etc. is main composite oxide, its part by weight adds a certain amount of graphite again through converting, and in the catalyst finished product that finally makes by each component of oxide and mass percent thereof is: NiO 30 ~ 50%, La
2O
31 ~ 5%, Al
2O
330 ~ 50%, MgO 12 ~ 20%, graphite 1 ~ 3%.
Compared with prior art, the invention has the beneficial effects as follows:
1, active component NiO is evenly distributed in the inner surface of catalyst, and the Ni crystal grain after former the going back has higher conversion ratio and selectivity;
2, La
2O
3Adding increased the decentralization of active constituent NiO, at high temperature grow inhibited for Ni crystal grain;
3, aluminum nitrate and magnesium nitrate form magnesium aluminate in precipitation process, and at high temperature can form magnesium aluminate spinel, have the transformationreation of inhibition effect, reduce CH
4Cracking and the directly synthetic CO of two CO
2The possibility of carbon distribution takes place.
4, provided by the inventionly be used for that oven gas and Straw Gas are mixed with high, active good, the Heat stability is good of the Catalyst for CO conversion ratio of artificial natural gas, anti-carbon nature is good, have good temperature resistance can, be convenient to commercial Application and promote.
The specific embodiment
Below in conjunction with the specific embodiment the present invention is made further detailed description, but embodiment of the present invention is not limited only to following embodiment.
Embodiment 1
Placing response still in water bath with thermostatic control is with 26.54gNi (NO
3)
26H
2O; 83.50gAl (NO
3)
39H
2O; 28.92gMg (NO
3)
26H
2O; 0.60gLa (NO
3)
36H
2O is mixed with 1L solution and adds in the agitated reactor, stirs, and adds 10% K when being heated to 68 ℃
2CO
3Solution keeps this temperature to carry out precipitation reaction and the final pH of adjusting value is 9.2.The resulting sediment of filtration washing is the catalyst semi-finished product.With the catalyst semi-finished product in drying box in 120 ℃ of dryings 5 hours; In Muffle furnace, calcined 4 hours down in 380 ℃; Burnt material (catalyst semi-finished product) and graphite put into according to material: graphite=100:2 (mass ratio) ball mill grinds and batch mixing, its mixture is all through 200 mesh sieves, the distilled water of adding 8%; After mixing, it is cylindric to process ￠ 5x5mm with the compression molding machine.
Each component and mass percent thereof are in the catalyst of present embodiment preparation: NiO30%, La
2O
31%, Al
2O
348.1%, MgO 18.9%, graphite 2%.
Embodiment 2
Placing response still in water bath with thermostatic control is with 44.24gNi (NO
3)
26H
2O; 50.13gAl (NO
3)
39H
2O; 17.35gMg (NO
3)
26H
2O; 3.02gLa (NO
3)
36H
2O is mixed with 1L solution and adds in the agitated reactor, stirs, and adds 12% K when being heated to 72 ℃
2CO
3Solution keeps this temperature to carry out precipitation reaction and the final pH of adjusting value is 9.5.The resulting sediment of filtration washing is the catalyst semi-finished product.With the catalyst semi-finished product in drying box in 150 ℃ of dryings 4 hours; In Muffle furnace, calcined 3 hours down in 450 ℃; Burnt material and graphite put into according to material: graphite=100:3 (mass ratio) ball mill grinds and batch mixing, its mixture adds 10% distilled water all through 200 mesh sieves; After mixing, it is cylindric to process ￠ 5x5mm with the compression molding machine.
Each component and mass percent thereof are in the catalyst of present embodiment preparation: NiO50%, La
2O
35%, Al
2O
329.8%, MgO12.2%, graphite 3%.
Embodiment 3
Placing response still in water bath with thermostatic control is with 35.39gNi (NO
3)
26H
2O; 66.85gAl (NO
3)
39H
2O; 23.14gMg (NO
3)
26H
2O; 1.8gLa (NO
3)
36H
2O is mixed with 1L solution and adds in the agitated reactor, stirs, and adds 10% K when being heated to 70 ℃
2CO
3Solution keeps this temperature to carry out precipitation reaction and the final pH of adjusting value is 9.2.The resulting sediment of filtration washing is the catalyst semi-finished product.With the catalyst semi-finished product in drying box in 120 ℃ of dryings 4 hours; In Muffle furnace, calcined 4 hours down in 400 ℃; Burnt material and graphite put into according to material: graphite=100:2 (mass ratio) ball mill grinds and batch mixing, its mixture adds 10% distilled water all through 200 mesh sieves; After mixing, it is cylindric to process ￠ 5x5mm with the compression molding machine.
Each component and mass percent thereof are in the catalyst of present embodiment preparation: NiO39.8%, La
2O
33%, Al
2O
339.2%, MgO 16%, graphite 2%.
In embodiment 1-3, K
2CO
3Effect be regulator solution pH value; The main effect of graphite and water is to make catalyst moulding more easily, and bonding tight, appearance has characteristics such as metallic luster.
Embodiment 4
With the granule of catalyst breakage to the 1 ~ 2mm of embodiment 1-3 preparation, getting the 10ml internal diameter of packing into respectively is the reaction tube of 17mm, and catalyst bed layer height 35mm carries out determination of activity to catalyst.
Select analyzer for use: gas chromatograph GC-1690 (chemical industry instrument and equipment dawn Co., Ltd of Hangzhou section)
Unstripped gas: CO
2+ H
2CO wherein
2: H
2=1:4 (volume ratio)
Under 350 ℃ of temperature, with the hydrogen pressure-raising to 0.6Mpa, reductase 12 hour, reduction air speed 15000h
-1, reduction finishes the back and feeds CO
2, adjustment CO
2: H
2=1:4 (volume ratio) pressure-raising is to 1.6Mpa, and respectively 500 ℃ of beds outlet temperatures, 570 ℃ determine the implication composition, and press conversion ratio %=(CO+CH
4)/(CO+CO
2+ CH
4) x100%, selectivity %=CH
4/ (CO+CH
4) x100% result of calculation, experimental result is seen table 1.
Table 1 determination of activity result (V%)
Temperature ℃ CO CH
4CO
2Conversion ratio % selectivity %
Embodiment 1 500 0.075 54.50 8.80 86.11 99.86
5700.69045.5411.26? 80.41? 98.51
Embodiment 2 500 0.050 54.01 8.80 86.00 99.91
5700.66044.7010.65 ?80.99 ?98.55
Embodiment 3 500 0.052 55.07 7.33 88.26 99.91
?5700.48047.539.34 83.71? 99.00
The unstripped gas of present embodiment is by CO
2And H
2Constitute, visible by table 1 data, any oven gas that makes by embodiment 1-3 and the catalyst of Straw Gas gaseous mixture system methane all have good activity and selectivity, and the catalyst surface that unloads after the test is totally carbon-free.
Embodiment 5
With the granule of catalyst breakage to the 1 ~ 2mm of embodiment 1-3 preparation, getting the 10ml internal diameter of packing into respectively is the reaction tube of 17mm, and catalyst bed layer height 35mm carries out determination of activity to catalyst.
Select analyzer for use: gas chromatograph GC-1690 (chemical industry instrument and equipment dawn Co., Ltd of Hangzhou section)
Unstripped gas: CO+H
2CO:H
2=1:4 (volume ratio)
Under 350 ℃ of temperature, with the hydrogen pressure-raising to 0.6Mpa, reductase 12 hour, reduction air speed 15000h
-1, reduction finishes the back and feeds CO, adjustment CO:H
2=1:4 (volume ratio) pressure-raising is to 1.6Mpa, and respectively 520 ℃ of beds outlet temperatures, 580 ℃ determine the implication composition, and press conversion ratio %=(CO
2+ CH
4)/(CO+CO
2+ CH
4) x100%, selectivity %=CH
4/ (CO
2+ CH
4) x100% result of calculation, experimental result is seen table 2.
Table 2 determination of activity result (V%)
Temperature ℃ CO CH
4CO
2Conversion ratio % selectivity %
Embodiment 1 520 0.196 44.862 0.196 99.57 99.57
5800.07948.0050? 99.84 ?100.00
Embodiment 2 520 0.160 45.256 0.160 99.65 99.65
?5800.06548.174?0? ?99.87 ?100.00
Embodiment 3 520 0.147 45.544 0.122 99.68 99.73
5800.05948.502?0 99.89? 100.00
Embodiment 6
With the granule of catalyst breakage to the 1 ~ 2mm of embodiment 1-3 preparation, getting the 10ml internal diameter of packing into respectively is the reaction tube of 17mm, and catalyst bed layer height 35mm carries out determination of activity to catalyst.
Select analyzer for use: gas chromatograph GC-1690 (chemical industry instrument and equipment dawn Co., Ltd of Hangzhou section)
Unstripped gas: adopt oven gas and Straw Gas mixing gas component to carry out distribution, its mist is formed as shown in table 3:
Table 3 oven gas and Straw Gas mixing gas component (V%)
Title CO CH
4CO
2H
2N
2
Content 16.58 9.99 19.97 50.35 3.11
Under 350 ℃ of temperature, with the hydrogen pressure-raising to 0.6Mpa, reductase 12 hour, reduction air speed 2000h
-1, reduction finishes the back and feeds water vapour and unstripped gas, breaks off hydrogen then, and pressure-raising is to 1.5Mpa gradually, and temperature rises to 520 ℃ of beds outlets, unstripped gas air speed 10000 h
-1, steam-to-gas ratio 0.2 carries out methanation reaction, record reaction result such as table 4:
Table 4 oven gas and Straw Gas gaseous mixture methanation reaction result (V%)
CO CH
4CO
2N
2CO conversion ratio % CH
4Selectivity
Embodiment 1 0.15 47.90 39.09 5.76 92.29 94.65
Embodiment 2 0.12 48.43 38.97 5.64 92.12 94.73
Embodiment 3 0.12 48.49 38.85 5.74 92.12 94.74
Data are visible from table; The gaseous mixture methanation catalyst of oven gas of the present invention and Straw Gas has the function that also has transformationreation in the methanation reaction function between bed, be good multifunction catalyst; After the running, the catalyst surface that unloads does not totally have carbon distribution.
The disclosed a kind of catalyst that is used for coal preparing natural gas methanator of prior art CN201110188574.2, raw gas pressure is 3.5MPa in this catalyst environment, the unstripped gas of its catalysis consists of: H
2, CO, N
2, CO
2, CH4; Its CO conversion ratio is between 69.4 ~ 77.0%.
Catalyst of the present invention in embodiment 4 to by CO
2And H
2When the gaseous mixture that constitutes carries out methanation reaction catalysis, CO
2Conversion ratio is between 69.4 ~ 77.0%; In embodiment 5 to by CO, H
2When the gaseous mixture that constitutes carried out methanation reaction catalysis, the CO conversion ratio was between 99.57 ~ 99.89; In embodiment 6, the conversion ratio of CO is greater than 92% in oven gas and the Straw Gas gaseous mixture methanation reaction, and the selectivity of methane is greater than 94%.Among the embodiment of the invention 4, the embodiment 5, raw gas pressure is 1.6Mpa in the catalyst environment, among the embodiment 6; Raw gas pressure is 1.5Mpa in the catalyst environment, and for raw gas pressure 3.5MPa in the existing catalyst environment, its catalytic reaction environment requirement is much lower; Thereby the requirement to consersion unit is also much lower, and the production security of reactor can be ensured further that catalyst of the present invention unstripped gas in catalytic environment requires under the lower pressure condition; Can guarantee the conversion ratio of CO in the unstripped gas equally; And therefore the conversion ratio of its CO adopted catalyst of the present invention when the conversion ratio of CO had catalyst now far above employing, and its activity is good; The CO conversion ratio is significantly increased with respect to prior art, more helps industrial applications.
Claims (3)
1. oven gas and Straw Gas are mixed with the catalyst of artificial natural gas, comprise carrier, active constituent and auxiliary agent, and it is characterized in that: said carrier is Al
2O
3, MgO, active component is NiO, auxiliary agent is La
2O
3, each component and mass percent thereof are in this catalyst: NiO 30～50%, La
2O
31～5%, Al
2O
330～50%, MgO 12～20%, graphite 1～3%.
2. a kind of oven gas according to claim 1 and Straw Gas are mixed with the catalyst of artificial natural gas, it is characterized in that: H in the mixed gaseous mixture of said oven gas and Straw Gas
2Mol ratio 3.0～4.0:1.0 with CO.
3. claim 1 or 2 described a kind of oven gas and Straw Gas are mixed with the Preparation of catalysts method of artificial natural gas, it is characterized in that: comprise the steps:
(1) precipitation reaction makes the catalyst semi-finished product: placing response still in water bath with thermostatic control is the Ni (NO of 26.54～44.24g/L with concentration
3)
26H
2The O aqueous solution; 50.13 the Al (NO of～83.50g/L
3)
39H
2The O aqueous solution; 17.35 the Mg (NO of～28.92g/L
3)
26H
2La (the NO of the O aqueous solution and 0.60～3.02g/L
3)
36H
2The O aqueous solution adds in the agitated reactor, adds precipitating reagent K when under stirring condition, being heated to 65～75 ℃
2CO
3To K
2CO
3Mass percent concentration be 10～12%, in whole precipitation reaction process, keep 68～70 ℃, regulator solution pH value to 9.0～9.5; The resulting sediment of filtration washing is the catalyst semi-finished product;
(2) drying: with catalyst semi-finished product under 120～150 ℃ of conditions dry 4～5 hours;
(3) calcining: with dried catalyst semi-finished product 300～450 ℃ temperature lower calcination 3～4 hours;
(4) mix: the catalyst semi-finished product after will calcine and graphite are by grinding in mass ratio 100:1～3 adding ball mills and mixing, and its mixture is all through 200 mesh sieves;
(5) compression moulding: the distilled water of adding 6～12% mixes back compression moulding and promptly obtains the catalyst finished product.
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|---|---|---|---|
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| CN104475119A (en) * | 2014-12-18 | 2015-04-01 | 中海石油气电集团有限责任公司 | CO2 high-temperature methanation catalyst, and preparation and use methods thereof |
| CN106179364A (en) * | 2015-05-07 | 2016-12-07 | 中国石油化工股份有限公司 | Preparation method for methanol purge gas synthesis LNG catalyst |
| CN108686666A (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 oven gas methane catalyst |
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| Publication number | Publication date |
|---|---|
| CN102614887B (en) | 2014-03-19 |
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