CN105080616B - A kind of preparation method of coke-oven gas methanation catalyst carrier - Google Patents
A kind of preparation method of coke-oven gas methanation catalyst carrier Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of coke-oven gas methanation catalyst carrier, belong to catalyst technical field.Catalyst carrier is obtained as follows：1）HY molecular sieves or the molecular sieves of silicalite 1 are heat-treated；2）Molecular sieve after heat treatment is mixed with one or more in gamma-alumina, aluminum stearate, aluminum nitrate；3）One or two mixing therein of triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, cellulose derivative, polyacrylamide, guar gum, ethylene glycol, polyethylene glycol, fatty acid polyethylene glycol ester, glycerine are added to said mixture, water is added, is mediated uniform；4）By the material granulation after kneading, particle is obtained, then dry particle；5）The particle of drying adds graphite to be well mixed, shaping；6）Tablet is by drying, then is calcined and obtains catalyst carrier.Using the method can obtained methanation catalyst carrier there is good hydrothermal stability and anti-carbon.
Description
Technical field
The invention belongs to catalysis technical field, and in particular to a kind of new side for preparing coke-oven gas methanation catalyst carrier
Method.
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
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, economic benefit higher is produced, help to form good circulation industrial chain.Produced by methanation with oven gas and closed
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 used as alternative motor fuels, particularly for taxi and public transport
The fields such as car, with larger price advantage.Therefore, there is coke-oven gas methanation synthetic natural gas important economic and society to anticipate
Justice.
Coke-oven gas methanation reaction belongs to strong exothermal reaction, and key reaction formula is as follows：
。
Because methanation reaction process balances constant is big, and unstripped gas CO, CO2Content is higher, reaction instantaneous exothermic heat amount compared with
Hurry up.Therefore, in addition to removing reaction heat in time using suitable technique, equipment, the good methanation catalyst of heat endurance is developed
Agent seems extremely important.And good catalyst carrier is to obtain the good methanation catalyst of heat endurance to obtain high thermal stability
It is crucial.
Methanation catalyst is generally with Al2O3, zirconium oxide, silica be carrier, the methane as disclosed in patent US 3933833
Change catalyst with high-purity gamma-Al2O3It is carrier, load active component nickel oxide and cobalt oxide.Disclosed in patent CN 1043639A
With zirconium oxide as carrier, nickel is active component to methanation catalyst, is urged to help with rare earth metal or alkaline-earth metal, or alkaline-earth metal
Agent.Methanation catalyst disclosed in patent CN 1043449A, nickel is active component, and rare earth metal and magnesium are co-catalyst, its
Remaining is aluminum oxide.These methanation catalysts are used in the methanation reaction of trace amounts of CO x, and reaction temperature is not high, reacting gas
Middle steam partial pressure is relatively low, and catalyst has good stability.But the carrier hydrothermal stability of these catalyst is poor, and also
It is faced with the carbon distribution problem in methanation reaction.
Molecular sieve is a kind of silica-alumina material with loose structure and regular pore canal, is had generally below 500 DEG C fine
Heat endurance and hydrothermal stability.HY, silicalite-1 molecular sieve are thermally treated resulting at a temperature of 120 DEG C ~ 700 DEG C
Molecular sieve, with good heat endurance and hydrothermal stability.Molecular sieve is widely used in the aspects such as sorbing material, catalytic cracking.
The content of the invention
The invention provides a kind of new method for preparing coke-oven gas methanation preparing natural gas catalyst carrier.Using the method
Can obtained methanation catalyst carrier there is good hydrothermal stability and anti-carbon.
Methanation catalyst carrier of the present invention is obtained as follows： 1）By HY molecular sieves or
Silicalite-1 molecular sieves are heat-treated；2）By the molecular sieve after heat treatment and gama-alumina, aluminum stearate, aluminum nitrate
In one or more mixing；3）Triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methylpent are added to said mixture
Alcohol, cellulose derivative, polyacrylamide, guar gum, ethylene glycol, polyethylene glycol, fatty acid polyethylene glycol ester, glycerine are therein
One or two mixing, add water, mediate uniform；4）By the material granulation after kneading, particle is obtained, then dry particle
It is dry；5）The particle of drying adds graphite to be well mixed, shaping；6）Tablet is by drying, then is calcined and obtains catalyst carrier.
Usually, in methanation catalyst carrier preparation method of the present invention, HY molecular sieves are carried out at 120 DEG C ~ 700 DEG C
The heat treatment of 1h ~ 3h；1h ~ 3h is calcined at 700 DEG C ~ 1200 DEG C and obtains catalyst carrier.
Using the methanation catalyst carrier high mechanical strength prepared by the present invention, good hydrothermal stability is adapted to higher
CO contents and reaction temperature higher under methanation reaction, can effectively prevent carbon deposit.
Specific embodiment
With reference to embodiment, the present invention is described in detail：
Embodiment 1：
1）600g HY molecular sieves are taken, is 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 well mixed；3）Well mixed material is added into 15g triethyl groups
Hexyl phosphoric acid, adds deionized water, mediates uniform；4）By the material granulation after kneading, the particle of good fluidity is obtained, then
Particle is dried at a temperature of 100 DEG C；5）The particle of drying adds graphite to be well mixed, compression molding；6）Tablet passes through drying,
Again catalyst carrier I is obtained in 700 DEG C of roastings.
Embodiment 2：
1）600g HY molecular sieves are taken, is heat-treated at 700 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 well mixed；3）Well mixed material is added into 15g triethyl groups
Hexyl phosphoric acid, adds deionized water, mediates uniform；4）By the material granulation after kneading, the particle of good fluidity is obtained, then
Particle is dried at a temperature of 160 DEG C；5）The particle of drying adds graphite to be well mixed, compression molding；6）Tablet passes through drying,
Again catalyst carrier II is obtained in 1200 DEG C of roastings.
Embodiment 3：
1）600g silicalite-1 molecular sieves are taken, is heat-treated at 120 DEG C, heat treatment time is 1h；2）At heat
18g gama-aluminas and 300g deionized waters are added in silicalite-1 molecular sieves after reason, is well mixed；3）To mix equal
Even material adds 15g triethyl group hexyl phosphoric acids, adds deionized water, mediates uniform；4）By the material granulation after kneading, obtain
To the particle of good fluidity, then particle is dried at a temperature of 100 DEG C；5）The particle of drying adds graphite to be well mixed, pressure
Sheetmolding；6）Tablet is by drying, then obtains catalyst carrier III in 700 DEG C of roastings.
Embodiment 4：
1）600g silicalite-1 molecular sieves are taken, is heat-treated at 700 DEG C, heat treatment time is 1h；2）At heat
18g gama-aluminas and 300g deionized waters are added in silicalite-1 molecular sieves after reason, is well mixed；3）To mix equal
Even material adds 15g triethyl group hexyl phosphoric acids, adds deionized water, mediates uniform；4）By the material granulation after kneading, obtain
To the particle of good fluidity, then particle is dried at a temperature of 160 DEG C；5）The particle of drying adds graphite to be well mixed, pressure
Sheetmolding；6）Tablet is by drying, then obtains catalyst carrier IV in 1200 DEG C of roastings.
Embodiment 5：
1）600g HY molecular sieves are taken, is heat-treated at 700 DEG C, heat treatment time is 1h；2）HY points after heat treatment
18g aluminum stearates and 300g deionized waters are added in son sieve, is well mixed；3）Well mixed material is added into 15g triethyl groups
Hexyl phosphoric acid, adds deionized water, mediates uniform；4）By the material granulation after kneading, the particle of good fluidity is obtained, then
Particle is dried at a temperature of 160 DEG C；5）The particle of drying adds graphite to be well mixed, compression molding；6）Tablet passes through drying,
Again catalyst carrier V is obtained in 1200 DEG C of roastings.
Embodiment 6：
1）600g HY molecular sieves are taken, is heat-treated at 700 DEG C, heat treatment time is 1h；2）HY points after heat treatment
18g aluminum nitrates and 300g deionized waters are added in son sieve, is well mixed；3）Material that will be well mixed add 15g triethyl groups oneself
Base phosphoric acid, adds deionized water, mediates uniform；4）By the material granulation after kneading, the particle of good fluidity is obtained, then will
Particle is dried at a temperature of 160 DEG C；5）The particle of drying adds graphite to be well mixed, compression molding；6）Tablet passes through drying, then
Catalyst carrier VI is obtained in 1200 DEG C of roastings.
Embodiment 7：
1）600g HY molecular sieves are taken, is heat-treated at 700 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 well mixed；3）Well mixed material is added into 15g second two
Alcohol, adds deionized water, mediates uniform；4）By the material granulation after kneading, the particle of good fluidity is obtained, then by particle
Dried at a temperature of 160 DEG C；5）The particle of drying adds graphite to be well mixed, compression molding；6）Tablet passes through dries, then
1200 DEG C of roastings obtain catalyst carrier VII.
0.5h in the immersion nickel nitrate solution of methanation catalyst carrier I, II, III, IV, V, VI, VII, takes out at 120 DEG C
Drying, then it is calcined 2h at 400 DEG C；7）Repeat step 6）, so that NiO load capacity reaches 10%, fixed bed tubular type is seated in respectively
In reactor, reaction condition is：Pressure 2.0MPa, oven gas gas composition H239.12, CH453.08, CO 1.18, CO2
6.30, N21.13, C2H61.93rd, gas space velocity is 5000 ~ 30000h-1, after 600 DEG C of reaction 500h, the activity holding of catalyst
Well, wherein CO conversion ratios are 100%, and methane selectively is 100%, and the catalytic mechanical intensity for removing is still very high, catalysis
The surface of agent does not have carbon distribution.
Claims (3)
1. a kind of preparation method of coke-oven gas methanation catalyst carrier, it is characterized in that being obtained as follows：1）By HY points
Son sieve or silicalite-1 molecular sieves are heat-treated, and at 120 DEG C ~ 700 DEG C, heat treatment time is molecular sieve heat treatment temperature
1h~3h；2）Molecular sieve after heat treatment is mixed with one or more of gama-alumina, aluminum stearate, aluminum nitrate；3）Upwards
State mixture and add triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, cellulose derivative, polyacrylamide, Gu
One or two mixing therein of that glue, ethylene glycol, polyethylene glycol, fatty acid polyethylene glycol ester, glycerine, add water, mediate
Uniformly；4）By the material granulation after kneading, particle is obtained, then dry particle；5）The particle of drying adds graphite mixing equal
It is even, shaping；6）Tablet is by drying, then is calcined and obtains catalyst carrier.
2. the preparation method of catalyst carrier according to claim 1, it is characterised in that catalyst carrier sintering temperature is 700
℃~1200℃。
3. the preparation method of catalyst carrier according to claim 1, it is characterised in that catalyst carrier roasting time be 1h ~
3h。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3988262A (en) * | 1974-07-03 | 1976-10-26 | Haldor Topsoe A/S | Methanation catalyst and process for preparing the catalyst |
| CN102327769A (en) * | 2011-06-13 | 2012-01-25 | 大连理工大学 | Methanation catalyst and application thereof |
| CN102335608A (en) * | 2010-07-28 | 2012-02-01 | 中国石油化工股份有限公司 | Preparation method of methanation catalyst active matrix |
| 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 |
| CN103131490A (en) * | 2011-12-02 | 2013-06-05 | 中国科学院大连化学物理研究所 | Technology of coke oven gas for methane production |
-
2014
- 2014-05-08 CN CN201410192133.3A patent/CN105080616B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3988262A (en) * | 1974-07-03 | 1976-10-26 | Haldor Topsoe A/S | Methanation catalyst and process for preparing the catalyst |
| CN102335608A (en) * | 2010-07-28 | 2012-02-01 | 中国石油化工股份有限公司 | Preparation method of methanation catalyst active matrix |
| CN102327769A (en) * | 2011-06-13 | 2012-01-25 | 大连理工大学 | Methanation catalyst and application thereof |
| 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 |
| CN103131490A (en) * | 2011-12-02 | 2013-06-05 | 中国科学院大连化学物理研究所 | Technology of coke oven gas for methane production |
Non-Patent Citations (1)
| Title |
|---|
| CO methanation activity and XPS studies of Pd supported on ZSM5 and Y-zeolites;N.C.Saha等;《Applied Catalysis》;19841231;第13卷(第1期);第102-108页 * |
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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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