CN106311352B - A kind of preparation method for oven gas preparing natural gas catalyst carrier - Google Patents
A kind of preparation method for oven gas preparing natural gas catalyst carrier Download PDFInfo
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Abstract
The invention belongs to catalysis technical fields, are related to a kind of preparation method for oven gas preparing natural gas catalyst carrier.Alkaline earth oxide, rare-earth metal nitrate and γ-Al is added after obtained washing of precipitate qualification by the soluble salt solutions with alkali neutralization magnesium in the carrier2O3It is mixed with beating together, material is using filter, drying, roasting, granulation, compression molding, then roasts to obtain catalyst carrier.The carrier has good hydrothermal stability, is suitble to using methane synthesizing catalyst prepared by the carrier containing C2The oven gas preparing natural gas methanation reaction of hydrocarbon, and have the characteristics that be not easy carbon deposit under high CO content.
Description
Technical field
The invention belongs to catalysis technical fields, are related to a kind of preparation side for oven gas preparing natural gas catalyst carrier
Method.
Background technique
In recent years, with " Shan gas is gone to the capital ", " the national level fuel gas transmission engineering such as West-east Gas is built up and is put into succession
It uses, the demand of natural gas is in explosive growth, and China will face the challenge of natural gas supply safety.
As a kind of good clean energy resource, the specific gravity in the energy-consuming in China increases natural gas year by year.For many years,
The yield of natural gas causes the import volume of natural gas to be significantly increased year by year far from meeting the needs of consumption.Therefore, people start
Concern produces natural gas using oven gas, to meet the increased requirement of natural gas.And China's annual generation about 1200 in recent years
Hundred million Nm3Oven gas, except coking is personal, civilian and business-purpose fuel, power generation in addition to, there are also quite a few direct emission, utilization rates
It is only about 55%, has not only wasted valuable resource, but also polluted environment.Synthetic natural gas is produced by methanation with oven gas
(SNG) compressed natural gas (CNG) or liquefied natural gas (LNG) are further produced, capacity usage ratio up to 80% or more, and
And its process is relatively easy, investment is lower, good in economic efficiency, has the very strong market competitiveness.It is continuous with crude oil price
Go up, gas price is also constantly rising violently, and CNG is especially led for taxi and bus etc. as alternative motor fuels
Domain has biggish price advantage.Therefore, coke-oven gas methanation synthetic natural gas has important economy and society meaning.
Coke-oven gas methanation reaction belongs to strong exothermal reaction, and key reaction formula is as follows:
Since methanation reaction process balances constant is big, and unstripped gas CO, CO2Content is higher, reaction instantaneous exothermic heat amount compared with
Fastly.Therefore, other than removing reaction heat in time using suitable technique, equipment, the good methanation catalyst of thermal stability is developed
Agent seems extremely important.
The country a long time ago just develops methanation catalyst, is mainly used for purified synthesis gas, such as Nan Hua group
The J105 that research institute develops is not easy to run at high temperature it is suitable for the methanation of low concentration oxycarbide in unstripped gas.China
The novel methanation catalyst prepared in patent CN200710146033.7 produces high concentration first for the methanation of synthesis gas depth
Alkane, after adding rare earth element, CO2It is hydroconverted into the reaction conversion ratio with higher of methane, but its reaction velocity, pressure
It is high；The coke-oven gas methanation catalyst prepared in CN200810046429.9 is used for coke-oven gas methanation SNG, reactivity
Height, but heat-resisting quantity is poor, and overtemperature inactivates easily in coke-oven gas methanation reaction process.
Summary of the invention
It is an object of that present invention to provide a kind of preparation methods for oven gas preparing natural gas catalyst carrier.
It is prepared via a method which: using provided by the present invention for the methane synthetic catalyst carrier of oven gas preparing natural gas
Alkaline earth oxide, rare earth metal nitric acid is added after obtained washing of precipitate qualification in the soluble salt solutions of alkali neutralization magnesium
Salt and γ-Al2O3It is mixed with beating together, material is using filter, drying, roasting, granulation, compression molding, then roasts and urged
Agent carrier.
Generally, steps are as follows for preparation method of the present invention: magnesium nitrate or magnesium sulfate are added to the water mixing by a.；B. it stirs
Under, solution is formed by with sodium bicarbonate or sodium carbonate neutralization procedure a；C. the obtained precipitating of step b is washed；D. to
Alkaline earth oxide, rare-earth metal nitrate and γ-Al is added in the qualified sediment of the washing that step c is obtained2O3Together into
Row is mixed with beating；E. material is using filter, drying, roasting；F. the binder that weight percentage 3% ~ 8% is added is granulated；
G. compression molding；H. it roasts to obtain methane synthetic catalyst carrier again.
Neutralization reaction endpoint pH should be controlled 7.0 ~ 8.0 in above-mentioned steps；
Neutralization reaction temperature is usually at 60 DEG C ~ 90 DEG C in above-mentioned steps；
First time maturing temperature general control in above-mentioned steps at 450 DEG C ~ 550 DEG C, generally control by second of maturing temperature
System is at 900 DEG C ~ 1100 DEG C；
Alkaline earth oxide includes one or more of calcium, magnesium, ba oxide in above-mentioned steps；
Rare-earth metal nitrate includes one or more of the nitrate of lanthanum, cerium, neodymium in above-mentioned steps；
Binder added by granulation process can be cellulose, methylcellulose, nitrocellulose, sesbania in above-mentioned steps
One of powder, cellulose acetate are several.
The carrier of the method for the present invention preparation has good hydrothermal stability, is suitble to contain using catalyst prepared by the carrier
There is C2The oven gas preparing natural gas methanation reaction of hydrocarbon, and have the characteristics that be not easy carbon deposit under high CO content.
Specific embodiment
The present invention is described in detail below with reference to embodiment.
Embodiment 1:(1) add water to mix the 800g magnesium nitrate；(2) under stirring, prepared sodium carbonate liquor is added and is walked
Neutralization reaction is carried out in rapid 1 solution formed, 60 DEG C of reaction temperature, reaction end pH value is controlled 8.0；(3) deionized water is used
The sediment that step 2 is obtained washs；(4) be added into step 3 obtains the qualified sediment of washing 90g calcium oxide,
30g magnesia and 300g γ-Al2O3It is mixed with beating together；(5) material is using filter, drying, 550 DEG C of roasting 2h；(6) add
Enter 3% methylcellulose to be granulated；(7) tabletted；(8) methane synthesizing catalyst is obtained in 1100 DEG C of roasting 2h again
Carrier I.
Embodiment 2:(1) add water to mix the 600g magnesium sulfate；(2) under stirring, prepared sodium bicarbonate solution is added
Neutralization reaction is carried out in the solution that step 1 is formed, 90 DEG C of reaction temperature, reaction end pH value is controlled 8.0；(3) deionization is used
The sediment that water obtains step 2 washs；(4) 90g oxidation is added into the qualified sediment of the washing that step 3 obtains
Calcium, 90g magnesia, 150g lanthanum nitrate and 350g γ-Al2O3It is mixed with beating together；(5) material is using filter, drying, 450
DEG C roasting 2h；(6) cellulose acetate of addition 5% is granulated；(7) tabletted；(8) first is obtained in 900 DEG C of roasting 2h again
Alkane synthesis catalytic agent carrier II.
Embodiment 3:(1) add water to mix the 600g magnesium sulfate；(2) under stirring, prepared sodium carbonate liquor is added and is walked
Neutralization reaction is carried out in rapid 1 solution formed, 80 DEG C of reaction temperature, reaction end pH value is controlled 7.5；(3) deionized water is used
The sediment that step 2 is obtained washs；(4) be added into step 3 obtains the qualified sediment of washing 150g barium monoxide,
90g magnesia, 150g cerous nitrate and 350g γ-Al2O3It is mixed with beating together；(5) material is using filter, drying, 500 DEG C
Roast 2h；(6) nitrocellulose of addition 4% is granulated；(7) tabletted；(8) methane is obtained in 900 DEG C of roasting 2h again
Synthesis catalytic agent carrier III.
Embodiment 4:(1) add water to mix the 800g magnesium nitrate；(2) under stirring, prepared sodium bicarbonate solution is added
Neutralization reaction is carried out in the solution that step 1 is formed, 80 DEG C of reaction temperature, reaction end pH value is controlled 7.0；(3) deionization is used
The sediment that water obtains step 2 washs；(4) 190g oxidation is added into the qualified sediment of the washing that step 3 obtains
Calcium, 150g lanthanum nitrate, 100g neodymium nitrate and 350g γ-Al2O3It is mixed with beating together；(5) material using filter, drying,
550 DEG C of roasting 2h；(6) sesbania powder of addition 8% is granulated；(7) tabletted；(8) first is obtained in 1000 DEG C of roasting 2h again
Alkane synthesis catalytic agent carrier IV.
Embodiment 5:(1) add water to mix the 800g magnesium nitrate；(2) under stirring, prepared sodium carbonate liquor is added and is walked
Neutralization reaction is carried out in rapid 1 solution formed, 70 DEG C of reaction temperature, reaction end pH value is controlled 7.5；(3) deionized water is used
The sediment that step 2 is obtained washs；(4) be added into step 3 obtains the qualified sediment of washing 90g calcium oxide,
50g lanthanum nitrate, 100g cerous nitrate and 350g γ-Al2O3It is mixed with beating together；(5) material is using filter, drying, 450 DEG C
Roast 2h；(6) sesbania powder of addition 8% is granulated；(7) tabletted；(8) methane is obtained in 1000 DEG C of roasting 2h again to close
At catalyst carrier V.
Embodiment 6: I, II, III, IV, V and g- of carrier Al is taken2O3Carrier is impregnated in nickel nitrate solution respectively, and Ni is made
The methane synthesizing catalyst I, II, III, IV, V, VI of content 16%.
Embodiment 7: by methane synthesizing catalyst I, II, III, IV, V, VI respectively loaded in fixed bed reactors, item is operated
Part are as follows: pressure 3.0MPa, 600 DEG C of reaction temperature, oven gas composition: CO:8%, CO2: 3%, H2: 52%, CH4: 30%, N2: 5.5%,
C2H6: remaining；After reacting 150 hours, as the result is shown: the hotspot location of methane synthesizing catalyst I, II, III, IV, V, VI is protected
Hold constant, catalyst, which is torn open after furnace, does not have carbon distribution through materialization detection catalyst surface；And the hotspot location of methane synthesizing catalyst VI
Have and obviously move down trend, catalyst, which is torn open after furnace, has obvious carbon deposition phenomenon through materialization detection catalyst surface.
It is obtained by above embodiments result, with the methane synthesizing catalyst and tradition of carrier preparation prepared by the method for the present invention
Alumina base catalyst compare, have better thermal stability, high temperature, high CO content, contain C2Have under the atmosphere of hydrocarbon
Better anti-carbon performance.
Claims (7)
1. a kind of preparation method for oven gas preparing natural gas catalyst carrier, it is characterised in that: solvable with alkali neutralization magnesium
Property salting liquid, by obtained washing of precipitate it is qualified after, alkaline earth oxide, rare-earth metal nitrate and γ-Al is added2O3One
It rises and is mixed with beating, material is using filter, drying, roasting, granulation, compression molding, then roasts to obtain catalyst carrier；Specifically
Be made as follows: magnesium nitrate or magnesium sulfate are added to the water mixing by a.；B. under stirring, with sodium bicarbonate or sodium carbonate
Neutralization procedure a is formed by solution；C. the obtained precipitating of step b is washed；D. the washing obtained to step c is qualified to sink
Alkaline earth oxide, rare-earth metal nitrate and γ-Al are added in starch2O3It is mixed with beating together；E. material using
Filter, dry, roasting: the binder that weight percentage 3% ~ 8% is added in f. is granulated；G. compression molding；H. it roasts to obtain again
For oven gas preparing natural gas catalyst carrier；
The alkaline earth oxide includes calcium, magnesium, ba oxide, wherein at least includes one of calcium, ba oxide or two
Kind.
2. support preparation method according to claim 1, it is characterised in that the control of neutralization reaction endpoint pH 7.0 ~
8.0。
3. support preparation method according to claim 1, it is characterised in that neutralization reaction temperature 60 C ~ 90 DEG C.
4. support preparation method according to claim 1, it is characterised in that rare-earth metal nitrate includes lanthanum, cerium, neodymium
One or more of nitrate.
5. support preparation method according to claim 1, it is characterised in that in step e maturing temperature control 450 DEG C ~
550℃。
6. support preparation method according to claim 1, it is characterised in that in step h maturing temperature control 900 DEG C ~
1100℃。
7. support preparation method according to claim 1, it is characterised in that binder added by granulation process be cellulose,
One of methylcellulose, nitrocellulose, sesbania powder, cellulose acetate are several.
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| CN114345351B (en) * | 2020-10-13 | 2024-05-14 | 中石化南京化工研究院有限公司 | Preparation method of synthetic gas methanation catalyst carrier |
| CN113713845A (en) * | 2021-09-03 | 2021-11-30 | 成都龙飞科技有限公司 | Preparation method of CO methanation catalyst in hydrogen-rich environment and catalyst prepared by method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4456703A (en) * | 1982-05-07 | 1984-06-26 | Exxon Research And Engineering Co. | High surface area nickel aluminate spinel catalyst for steam reforming |
| CN102350375A (en) * | 2011-08-17 | 2012-02-15 | 中国石油化工集团公司 | Preparation method of methane synthetic catalyst carrier |
| CN102500387A (en) * | 2011-11-17 | 2012-06-20 | 中国石油化工股份有限公司 | Catalyst for preparing substitute natural gas by using coal based synthesis gas, and preparation method thereof |
| CN103055876A (en) * | 2013-01-22 | 2013-04-24 | 新地能源工程技术有限公司 | Preparation method of wide-temperature methanation catalyst |
| CN103861599A (en) * | 2012-12-17 | 2014-06-18 | 中国石油化工股份有限公司 | Catalyst used for preparing substitute natural gas from coal, and preparation method thereof |
-
2015
- 2015-06-19 CN CN201510343626.7A patent/CN106311352B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4456703A (en) * | 1982-05-07 | 1984-06-26 | Exxon Research And Engineering Co. | High surface area nickel aluminate spinel catalyst for steam reforming |
| CN102350375A (en) * | 2011-08-17 | 2012-02-15 | 中国石油化工集团公司 | Preparation method of methane synthetic catalyst carrier |
| CN102500387A (en) * | 2011-11-17 | 2012-06-20 | 中国石油化工股份有限公司 | Catalyst for preparing substitute natural gas by using coal based synthesis gas, and preparation method thereof |
| CN103861599A (en) * | 2012-12-17 | 2014-06-18 | 中国石油化工股份有限公司 | Catalyst used for preparing substitute natural gas from coal, and preparation method thereof |
| CN103055876A (en) * | 2013-01-22 | 2013-04-24 | 新地能源工程技术有限公司 | Preparation method of wide-temperature methanation catalyst |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |
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