CN105080591B - A kind of preparation method of coke-oven gas methanation catalyst - Google Patents
A kind of preparation method of coke-oven gas methanation catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of coke-oven gas methanation catalyst, belong to catalysis technical field, a kind of preparation method of coke-oven gas methanation catalyst, it is characterised in that catalyst is made as follows：1）HY molecular sieves are heat-treated, molecular sieve USY is obtained；2）USY molecular sieve is mixed with the one or more in gamma-alumina, stearic acid, odium stearate, aluminum stearate, water is added, mediated uniform；3）By the material granulation after kneading, then particle is dried；4）The particle of drying adds graphite and is well mixed, shaping；5）Tablet is by drying, then is calcined and obtains catalyst carrier；6）Prepare and contain nickel nitrate and lanthanum nitrate, potassium nitrate（Or potassium carbonate）, cerous nitrate（Or cerous nitrate）One or more kinds of solution, the catalyst carrier of above-mentioned preparation is immersed in solution；7）Catalyst is made by drying, roasting.There is good hydrothermal stability and anti-carbon using methanation catalyst made from this method.
Description
Technical field
The invention belongs to catalysis technical field, and in particular to a kind of new method for preparing coke-oven gas methanation catalyst.
Background technology
With being continuously increased for natural gas demand and import volume, China will face the challenge of natural gas supply safety, and
China is annual in recent years to produce about 120,000,000,000 Nm3Oven gas a, part is used for generating electricity, and a part is used for hydrogen from methyl alcohol processed, also has
Quite a few is directly discharged, and its utilization rate is about 55%, therefore can effectively reclaim profit using oven gas preparing natural gas project
With resource, higher economic benefit is produced, helps to form good circulation industrial chain.Produced and closed by methanation with oven gas
Compressed natural gas (CNG) or liquefied natural gas (LNG) are further produced into natural gas (SNG), its capacity usage ratio is up to 80%
More than, and its flow is relatively easy, invest relatively low, good in economic efficiency, with the very strong market competitiveness.With crude oil price
Rise steadily, gas price is also constantly rising violently, and CNG is as alternative motor fuels, particularly for taxi and public transport
The fields such as car, with larger price advantage.Therefore, coke-oven gas methanation synthetic natural gas has important economy and society's meaning
Justice.
Methanation catalyst is generally with Al2O3For carrier, methanation catalyst is with high-purity as disclosed in patent US 3933833
γ-Al2O3For carrier, load active component nickel oxide and cobalt oxide.Methanation catalyst disclosed in patent CN 1043639A with
Al2O3For carrier, nickel is active component, and with rare earth metal or alkaline-earth metal, or alkaline-earth metal is co-catalyst.Patent CN
Methanation catalyst disclosed in 1043449A, nickel is active component, and rare earth metal and magnesium are co-catalyst, and remaining is aluminum oxide.
These methanation catalysts are used, reaction temperature is not high using aluminum oxide as carrier in trace amounts of CO x methanation reaction, reaction
Steam partial pressure is relatively low in gas, and catalyst has good stability.But the carrier hydrothermal stability of these catalyst is poor, and
And also face the carbon distribution problem in methanation reaction.HY molecular sieves carry out being thermally treated resulting in super at a temperature of 120 DEG C ~ 700 DEG C
Stable molecular sieve USY, with good heat endurance and hydrothermal stability.
The content of the invention
The invention provides a kind of method for preparing coke-oven gas methanation preparing natural gas catalyst.It can be made using this method
Methanation catalyst there is good hydrothermal stability and anti-carbon.
A kind of preparation method of coke-oven gas methanation catalyst, it is characterised in that catalyst is made as follows：1）
HY molecular sieves are being heat-treated, molecular sieve USY is obtained；2）By USY molecular sieve and gama-alumina, stearic acid, stearic acid
One or more kinds of mixing in sodium, aluminum stearate, add water, mediate uniform；3）By the material granulation after kneading, then
Particle is dried；4）The particle of drying adds graphite and is well mixed, shaping；5）Tablet is by drying, then is calcined and obtains catalyst
Carrier；6）Prepare and contain nickel nitrate and lanthanum nitrate, potassium nitrate（Or potassium carbonate）, cerous nitrate（Or cerous nitrate）It is a kind of or it is a kind of with
On solution, the catalyst carrier of above-mentioned preparation is immersed in solution；7）Catalyst is made by drying, roasting.
Usually, in method for preparing catalyst of the present invention, 1h ~ 3h heat is carried out to HY molecular sieves at 120 DEG C ~ 700 DEG C
Processing；1h ~ 3h is calcined at 700 DEG C ~ 1200 DEG C and obtains catalyst carrier；Carrier impregnates 0.5h ~ 3h in mixed solution, takes out
Dried at 120 DEG C；400 DEG C ~ 600 DEG C of the sintering temperature of catalyst.
The preparation method of the catalyst, carrier can be with repeated impregnations repeatedly, until the NiO contents in catalyst reach 10
~25%。
Using the methanation catalyst high mechanical strength prepared by the present invention, the stability of catalyst is good, hydrothermal stability
It is good, it is adapted to the methanation reaction under higher CO contents and higher reaction temperature, can effectively prevents carbon deposit.
Embodiment
With reference to embodiment, the present invention is described in detail：
Embodiment 1：
1）600g HY molecular sieves are taken, are heat-treated at 120 DEG C, heat treatment time is 1h；2）HY points after heat treatment
18g gama-aluminas and 300g deionized waters are added in son sieve, is mediated uniform；3）Uniform material granulation will be mediated into particle diameter about
For 1.2mm particle, in 120 DEG C of dry 3h；4）The particle of drying adds 12g graphite and is well mixed, by tabletting machine into
Ф 5 × 5 cylinder particle；5）Tablet obtains preparing the carrier required for catalyst by 700 DEG C of DEG C of roastings；6）Carrier is soaked
Enter 0.5h in nickel nitrate solution, take out and dried at 120 DEG C, then 2h is calcined at 400 DEG C；7）Repeat step 6）, so that NiO is negative
Carrying capacity reaches 10%, obtains catalyst I.
Embodiment 2：
1）600g HY molecular sieves are taken, are heat-treated at 700 DEG C, heat treatment time is 3h；2）HY points after heat treatment
18g gama-aluminas and 300g deionized waters are added in son sieve, is mediated uniform；3）Uniform material granulation will be mediated into particle diameter about
For 1.2mm particle, in 120 DEG C of dry 5h；4）The particle of drying adds 12g graphite and is well mixed, by tabletting machine into
Ф 5 × 5 cylinder particle；5）Tablet obtains preparing the carrier required for catalyst by 1200 DEG C of roastings；6）Carrier is soaked
Enter 3h in the solution of nickel nitrate and lanthanum nitrate, take out and dried at 120 DEG C, then 4h is calcined at 600 DEG C；7）Repeat step 6）,
So that NiO load capacity reaches 25%, catalyst II is obtained.
Embodiment 3：
1）600g HY molecular sieves are taken, are heat-treated at 500 DEG C, heat treatment time is 2h；2）HY points after heat treatment
18g gama-aluminas and 300g deionized waters are added in son sieve, is mediated uniform；3）Uniform material granulation will be mediated into particle diameter about
For 1.2mm particle, in 120 DEG C of dry 4h；4）The particle of drying adds 12g graphite and is well mixed, by tabletting machine into
Ф 5 × 5 cylinder particle；5）Tablet obtains preparing the carrier required for catalyst by 1100 DEG C of roastings；6）Carrier is soaked
Enter nickel nitrate, potassium nitrate（Or potassium carbonate）With 2h in the solution of lanthanum nitrate, take out and dried at 120 DEG C, then be calcined at 550 DEG C
3h；7）Repeat step 6）, so that NiO load capacity reaches 15%, obtain catalyst III.
Embodiment 4：
1）600g HY molecular sieves are taken, are heat-treated at 700 DEG C, heat treatment time is 2h；2）HY points after heat treatment
18g gama-aluminas and 300g deionized waters are added in son sieve, is mediated uniform；3）Uniform material granulation will be mediated into particle diameter about
For 1.2mm particle, in 120 DEG C of dry 3h；4）The particle of drying adds 12g graphite and is well mixed, by tabletting machine into
Ф 5 × 5 cylinder particle；5）Tablet obtains preparing the carrier required for catalyst by 700 DEG C of roastings；6）Carrier is immersed
Nickel nitrate, potassium nitrate, cerous nitrate（Or cerous nitrate）With 3h in the solution of lanthanum nitrate, take out and dried at 120 DEG C, then 400
2h is calcined at DEG C；7）Repeat step 6）, so that NiO load capacity reaches 25%, obtain catalyst IV.
Embodiment 5：
1）600g HY molecular sieves are taken, are heat-treated at 700 DEG C, heat treatment time is 2h；2）HY points after heat treatment
18g stearic acid and 300g deionized waters are added in son sieve, is mediated uniform；3）It is about by uniform material granulation is mediated into particle diameter
1.2mm particle, in 120 DEG C of dry 3h；4）The particle of drying adds 12g graphite and is well mixed, by tabletting machine into Ф 5
× 5 cylinder particle；5）Tablet obtains preparing the carrier required for catalyst by 700 DEG C of roastings；6）Carrier is immersed into nitre
Sour nickel, potassium nitrate, cerous nitrate（Or cerous nitrate）With 3h in the solution of lanthanum nitrate, take out and dried at 120 DEG C, then at 400 DEG C
Lower roasting 2h；7）Repeat step 6）, so that NiO load capacity reaches 25%, obtain catalyst V.
Embodiment 6：
1）600g HY molecular sieves are taken, are heat-treated at 700 DEG C, heat treatment time is 2h；2）HY points after heat treatment
18g odium stearate and 300g deionized waters are added in son sieve, is mediated uniform；3）It is about by uniform material granulation is mediated into particle diameter
1.2mm particle, in 120 DEG C of dry 3h；4）The particle of drying adds 12g graphite and is well mixed, by tabletting machine into Ф 5
× 5 cylinder particle；5）Tablet obtains preparing the carrier required for catalyst by 700 DEG C of roastings；6）Carrier is immersed into nitre
Sour nickel, potassium nitrate, cerous nitrate（Or cerous nitrate）With 3h in the solution of lanthanum nitrate, take out and dried at 120 DEG C, then at 400 DEG C
Lower roasting 2h；7）Repeat step 6）, so that NiO load capacity reaches 25%, obtain catalyst VI.
Embodiment 7：
1）600g HY molecular sieves are taken, are heat-treated at 700 DEG C, heat treatment time is 2h；2）HY points after heat treatment
18g aluminum stearates and 300g deionized waters are added in son sieve, is mediated uniform；3）It is about by uniform material granulation is mediated into particle diameter
1.2mm particle, in 120 DEG C of dry 3h；4）The particle of drying adds 12g graphite and is well mixed, by tabletting machine into Ф 5
× 5 cylinder particle；5）Tablet obtains preparing the carrier required for catalyst by 700 DEG C of roastings；6）Carrier is immersed into nitre
Sour nickel, potassium nitrate, cerous nitrate（Or cerous nitrate）With 3h in the solution of lanthanum nitrate, take out and dried at 120 DEG C, then at 400 DEG C
Lower roasting 2h；7）Repeat step 6）, so that NiO load capacity reaches 25%, obtain catalyst VII.
Methanation catalyst I, II, III, IV, V, VI, VII is seated in fixed-bed tube reactor respectively, reaction condition
For：Pressure 2.0MPa, oven gas gas composition H239.12, CH453.08, CO 1.18, CO26.30, N21.13, C2H6
1.93rd, gas space velocity is 5000 ~ 30000h-1, 600 DEG C are reacted after 500h, and the activity of catalyst keeps good, wherein CO conversion ratios
For 100%, methane selectively is 100%, and the catalytic mechanical intensity removed is still very high, and the surface of catalyst does not have carbon distribution.
Pass through high temperature, prolonged methanation reaction, the first still done well by the standby catalyst of patent system of the present invention
The carbon analysis shows of rear sample are drawn off after Alkylating Activity and stability, test, sample does not have obvious carbon distribution.
Claims (6)
1. a kind of preparation method of coke-oven gas methanation catalyst, it is characterised in that catalyst is made as follows：1）Will
HY molecular sieves are heat-treated, obtain molecular sieve USY, HY molecular sieve heat treatment temperature 120 DEG C ~ 700 DEG C, heat treatment time
In 1h ~ 3h；2）USY molecular sieve is mixed with one or more of gama-alumina, stearic acid, odium stearate, aluminum stearate, then
Water is added, is mediated uniform；3）By the material granulation after kneading, then particle is dried；4）The particle of drying adds graphite mixing
Uniformly, it is molded；5）Tablet is by drying, then is calcined and obtains catalyst carrier；6）Prepare and contain nickel nitrate and lanthanum nitrate, nitric acid
Potassium, potassium carbonate, cerous nitrate, more than one mixed solution of cerous nitrate, the catalyst carrier of above-mentioned preparation are immersed in molten
In liquid；7）Catalyst is made by drying, roasting.
2. the preparation method of catalyst according to claim 1, it is characterised in that catalyst carrier is in 700 DEG C ~ 1200 DEG C roastings
Burn.
3. the preparation method of catalyst according to claim 1, it is characterised in that catalyst carrier is calcined 1h ~ 3h.
4. the preparation method of catalyst according to claim 1, it is characterised in that carrier impregnated in mixed solution 0.5h ~
3h。
5. the preparation method of catalyst according to claim 1, it is characterised in that the sintering temperature 400 DEG C ~ 600 of catalyst
℃。
6. the preparation method of catalyst according to claim 1, it is characterised in that repeated impregnations repeatedly, until in catalyst
NiO contents reach 10% ~ 25%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500379A (en) * | 2011-11-17 | 2012-06-20 | 中国石油化工股份有限公司 | Catalyst for methanation and preparation method thereof |
| CN102585950A (en) * | 2012-02-27 | 2012-07-18 | 四川亚连科技有限责任公司 | Method for preparing synthetic natural gas by coke oven gas in combination with straw gas |
| CN103157475A (en) * | 2013-03-22 | 2013-06-19 | 北京神雾环境能源科技集团股份有限公司 | Catalyst for tri-reforming of coke oven gas and preparation method of catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500379A (en) * | 2011-11-17 | 2012-06-20 | 中国石油化工股份有限公司 | Catalyst for methanation and preparation method thereof |
| CN102585950A (en) * | 2012-02-27 | 2012-07-18 | 四川亚连科技有限责任公司 | Method for preparing synthetic natural gas by coke oven gas in combination with straw gas |
| CN103157475A (en) * | 2013-03-22 | 2013-06-19 | 北京神雾环境能源科技集团股份有限公司 | Catalyst for tri-reforming of coke oven gas and preparation method of catalyst |
Non-Patent Citations (1)
| Title |
|---|
| CO2 hydrogenation into CH4 on NiHNaUSY zeolites;I. GRACA 等;《Applied Catalysis B:Environmental》;20130820;第147卷;摘要第1-2行、倒数第1-6行 * |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Co-patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Patentee after: China Petroleum & Chemical Corp. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Co-patentee before: Nanhua Group Research Institute Patentee before: China Petroleum & Chemical Corp. |
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