CN105080616A - Preparation method of catalyst carrier through methanation of coke oven gas - Google Patents
Preparation method of catalyst carrier through methanation of coke oven gas Download PDFInfo
- Publication number
- CN105080616A CN105080616A CN201410192133.3A CN201410192133A CN105080616A CN 105080616 A CN105080616 A CN 105080616A CN 201410192133 A CN201410192133 A CN 201410192133A CN 105080616 A CN105080616 A CN 105080616A
- Authority
- CN
- China
- Prior art keywords
- catalyst carrier
- molecular sieve
- mixture
- preparation
- heat treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a catalyst carrier through the methanation of coke oven gas, and belongs to the technical field of catalysts. The catalyst carrier is prepared through the following steps: 1) performing heat treatment on an HY molecular sieve or a silicalite-1 molecular sieve; 2) mixing the molecular sieve after the heat treatment with one or more than one kind of gamma-aluminum oxide, aluminum stearate and aluminum nitrate so as to obtain a mixture; 3) mixing the mixture with one or two kinds of tri-ethylhexyl phosphate, sodium dodecyl sulfate, methyl anyl alcohol, a cellulose derivative, polyacrylamide, gul glue, ethanediol, polyethylene glycol, fatty acid polyglycol ester and glycerine so as to obtain a new mixture, adding water to a new mixture, and uniformly kneading the new mixture and the water so as to obtain kneaded materials; 4) pelletizing the kneaded materials so as to obtain particles, and baking the particles; 5) adding graphite to the baked particles, uniformly mixing the baked particles and the graphite so as to obtain a third mixture, and flattening the third mixture so as to form tablets; and 6) baking the tablets, and roasting the baked tablets once more so as to obtain the catalyst carrier. The methanation catalyst carrier prepared by the method has favorable hydrothermal stability and carbon deposition resistance.
Description
Technical field
The invention belongs to catalysis technical field, be specifically related to a kind of new method preparing coke-oven gas methanation catalyst carrier.
Background technology
Along with the continuous increase of natural gas demand and import volume, China will face the challenge of natural gas supply safety, and China produces about 1,200 hundred million Nm in recent years every year
3oven gas, a part is used for generating, and a part is used for hydrogen from methyl alcohol processed, also have quite a few directly to discharge, its utilization rate is about 55%, therefore utilizes oven gas preparing natural gas project effectively can recycle resource, produce higher economic benefit, contribute to forming good circulation industrial chain.Compressed natural gas (CNG) or liquefied natural gas (LNG) is produced again further by methanation production synthetic natural gas (SNG) with oven gas, its capacity usage ratio can reach more than 80%, and its flow process is relatively simple, investment is lower, good in economic efficiency, has the very strong market competitiveness.Along with rising steadily of crude oil price, gas price is also constantly rising violently, and CNG is as alternative motor fuels, especially for the field such as taxi and bus, has larger price advantage.Therefore, coke-oven gas methanation synthetic natural gas has important economy and social effect.
Coke-oven gas methanation reaction belongs to strong exothermal reaction, and key reaction formula is as follows:
.
Because methanation reaction process balances constant is large, and unstripped gas CO, CO
2content is higher, and reaction instantaneous exothermic heat amount is very fast.Therefore, except adopting suitable technique, equipment to remove in time except reaction heat, the methanation catalyst of development Heat stability is good seems extremely important.And obtain the key that the good catalyst carrier of high thermal stability is the methanation catalyst obtaining Heat stability is good.
Methanation catalyst is usually with Al
2o
3, zirconia, silica be carrier, disclosed in patent US3933833, methanation catalyst is with high-purity gamma-Al
2o
3for carrier, load active component nickel oxide and cobalt oxide.Methanation catalyst disclosed in patent CN1043639A take zirconia as carrier, and nickel is active component, and with rare earth metal or alkaline-earth metal, or alkaline-earth metal is co-catalyst.Methanation catalyst disclosed in patent CN1043449A, nickel is active component, and rare earth metal and magnesium are co-catalyst, and all the other are aluminium oxide.These methanation catalysts use in the methanation reaction of trace amounts of CO x, and reaction temperature is not high, and in reacting gas, steam partial pressure is lower, and catalyst has good stability.But the carrier hydrothermal stability of these catalyst is poor, and be faced with the carbon distribution problem in methanation reaction.
Molecular sieve is a kind of silica-alumina material with loose structure Sum fanction duct, usually below 500 DEG C, has good heat endurance and hydrothermal stability.HY, silicalite-1 molecular sieve is heat-treated and is obtained molecular sieve at 120 DEG C ~ 700 DEG C temperature, has good heat endurance and hydrothermal stability.The aspects such as molecular sieve is widely used in sorbing material, catalytic cracking.
Summary of the invention
The invention provides a kind of new method preparing coke-oven gas methanation preparing natural gas catalyst carrier.The methanation catalyst carrier utilizing the method to obtain has good hydrothermal stability and anti-carbon.
Methanation catalyst carrier of the present invention obtains as follows: 1) HY molecular sieve or silicalite-1 molecular sieve are heat-treated; 2) molecular sieve after heat treatment is mixed with one or more in gama-alumina, aluminum stearate, aluminum nitrate; 3) one or both mixing wherein 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, add water again, mediate evenly; 4) by the material granulation after kneading, obtain particle, then particle is dried; 5) particle of drying adds graphite and mixes, shaping; 6) tablet is through drying, then roasting obtains catalyst carrier.
Usually, in methanation catalyst carrier preparation method of the present invention, HY molecular sieve is carried out to the heat treatment of 1h ~ 3h at 120 DEG C ~ 700 DEG C; At 700 DEG C ~ 1200 DEG C, roasting 1h ~ 3h obtains catalyst carrier.
Adopt methanation catalyst carrier mechanical strength prepared by the present invention high, good hydrothermal stability, be adapted at methanation reaction under higher CO content and higher reaction temperature, effectively can prevent carbon deposit.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail:
Embodiment 1:
1) get 600gHY molecular sieve, heat-treat at 120 DEG C, heat treatment time is 1h; 2) add 18g gama-alumina and 300g deionized water in the HY molecular sieve after heat treatment, mix; 3) material mixed is added 15g triethyl group hexyl phosphoric acid, then add deionized water, mediate evenly; 4) by the material granulation after kneading, obtain the particle of good fluidity, then particle is dried at 100 DEG C of temperature; 5) particle of drying adds graphite and mixes, compression molding; 6) tablet is through drying, then obtains catalyst carrier I 700 DEG C of roastings.
Embodiment 2:
1) get 600gHY molecular sieve, heat-treat at 700 DEG C, heat treatment time is 1h; 2) add 18g gama-alumina and 300g deionized water in the HY molecular sieve after heat treatment, mix; 3) material mixed is added 15g triethyl group hexyl phosphoric acid, then add deionized water, mediate evenly; 4) by the material granulation after kneading, obtain the particle of good fluidity, then particle is dried at 160 DEG C of temperature; 5) particle of drying adds graphite and mixes, compression molding; 6) tablet is through drying, then obtains catalyst carrier II 1200 DEG C of roastings.
Embodiment 3:
1) get 600gsilicalite-1 molecular sieve, heat-treat at 120 DEG C, heat treatment time is 1h; 2) add 18g gama-alumina and 300g deionized water in the silicalite-1 molecular sieve after heat treatment, mix; 3) material mixed is added 15g triethyl group hexyl phosphoric acid, then add deionized water, mediate evenly; 4) by the material granulation after kneading, obtain the particle of good fluidity, then particle is dried at 100 DEG C of temperature; 5) particle of drying adds graphite and mixes, compression molding; 6) tablet is through drying, then obtains catalyst carrier III 700 DEG C of roastings.
Embodiment 4:
1) get 600gsilicalite-1 molecular sieve, heat-treat at 700 DEG C, heat treatment time is 1h; 2) add 18g gama-alumina and 300g deionized water in the silicalite-1 molecular sieve after heat treatment, mix; 3) material mixed is added 15g triethyl group hexyl phosphoric acid, then add deionized water, mediate evenly; 4) by the material granulation after kneading, obtain the particle of good fluidity, then particle is dried at 160 DEG C of temperature; 5) particle of drying adds graphite and mixes, compression molding; 6) tablet is through drying, then obtains catalyst carrier IV 1200 DEG C of roastings.
Embodiment 5:
1) get 600gHY molecular sieve, heat-treat at 700 DEG C, heat treatment time is 1h; 2) add 18g aluminum stearate and 300g deionized water in the HY molecular sieve after heat treatment, mix; 3) material mixed is added 15g triethyl group hexyl phosphoric acid, then add deionized water, mediate evenly; 4) by the material granulation after kneading, obtain the particle of good fluidity, then particle is dried at 160 DEG C of temperature; 5) particle of drying adds graphite and mixes, compression molding; 6) tablet is through drying, then obtains catalyst carrier V 1200 DEG C of roastings.
Embodiment 6:
1) get 600gHY molecular sieve, heat-treat at 700 DEG C, heat treatment time is 1h; 2) add 18g aluminum nitrate and 300g deionized water in the HY molecular sieve after heat treatment, mix; 3) material mixed is added 15g triethyl group hexyl phosphoric acid, then add deionized water, mediate evenly; 4) by the material granulation after kneading, obtain the particle of good fluidity, then particle is dried at 160 DEG C of temperature; 5) particle of drying adds graphite and mixes, compression molding; 6) tablet is through drying, then obtains catalyst carrier VI 1200 DEG C of roastings.
Embodiment 7:
1) get 600gHY molecular sieve, heat-treat at 700 DEG C, heat treatment time is 1h; 2) add 18g gama-alumina and 300g deionized water in the HY molecular sieve after heat treatment, mix; 3) material mixed is added 15g ethylene glycol, then add deionized water, mediate evenly; 4) by the material granulation after kneading, obtain the particle of good fluidity, then particle is dried at 160 DEG C of temperature; 5) particle of drying adds graphite and mixes, compression molding; 6) tablet is through drying, then obtains catalyst carrier VII 1200 DEG C of roastings.
Methanation catalyst carrier I, II, III, IV, V, VI, VII immerses 0.5h in nickel nitrate solution, takes out and dries at 120 DEG C, then at 400 DEG C roasting 2h; 7) repeat step 6), to make NiO load capacity reach 10%, be seated in fixed-bed tube reactor respectively, reaction condition is: pressure 2.0MPa, oven gas gas composition H
239.12, CH
453.08, CO1.18, CO
26.30, N
21.13, C
2h
61.93, gas space velocity is 5000 ~ 30000h
-1, after 600 DEG C of reaction 500h, the activity of catalyst keeps good, and wherein CO conversion ratio is 100%, and methane selectively is 100%, and the catalytic mechanical intensity removed is still very high, and the surface of catalyst does not have carbon distribution.
Claims (5)
1. a preparation method for coke-oven gas methanation catalyst carrier, is characterized in that obtaining as follows: 1) HY molecular sieve or silicalite-1 molecular sieve are heat-treated; 2) molecular sieve after heat treatment is mixed with one or more in gama-alumina, aluminum stearate, aluminum nitrate; 3) one or both mixing wherein 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, add water again, mediate evenly; 4) by the material granulation after kneading, obtain particle, then particle is dried; 5) particle of drying adds graphite and mixes, shaping; 6) tablet is through drying, then roasting obtains catalyst carrier.
2. the preparation method of catalyst carrier according to claim 1, is characterized in that molecular sieve heat treatment temperature is at 120 DEG C ~ 700 DEG C.
3. the preparation method of catalyst carrier according to claim 1, is characterized in that molecular sieve heat treatment time is 1h ~ 3h.
4. the preparation method of catalyst carrier according to claim 1, is characterized in that catalyst carrier sintering temperature is 700 DEG C ~ 1200 DEG C.
5. the preparation method of catalyst carrier according to claim 1, is characterized in that catalyst carrier roasting time is 1h ~ 3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410192133.3A CN105080616B (en) | 2014-05-08 | 2014-05-08 | A kind of preparation method of coke-oven gas methanation catalyst carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410192133.3A CN105080616B (en) | 2014-05-08 | 2014-05-08 | A kind of preparation method of coke-oven gas methanation catalyst carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105080616A true CN105080616A (en) | 2015-11-25 |
| CN105080616B CN105080616B (en) | 2017-07-11 |
Family
ID=54562480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410192133.3A Active CN105080616B (en) | 2014-05-08 | 2014-05-08 | A kind of preparation method of coke-oven gas methanation catalyst carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105080616B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108435242A (en) * | 2018-03-30 | 2018-08-24 | 中国石油化工股份有限公司 | Catalyst and preparation method thereof for phthalic acid ester selective hydrogenation |
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 |
|---|
| N.C.SAHA等: "CO methanation activity and XPS studies of Pd supported on ZSM5 and Y-zeolites", 《APPLIED CATALYSIS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108435242A (en) * | 2018-03-30 | 2018-08-24 | 中国石油化工股份有限公司 | Catalyst and preparation method thereof for phthalic acid ester selective hydrogenation |
| CN108435242B (en) * | 2018-03-30 | 2021-01-01 | 中国石油化工股份有限公司 | Catalyst for selective hydrogenation reaction of phthalic acid ester and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105080616B (en) | 2017-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106365995A (en) | Methyl acetate production method | |
| CN102500379A (en) | Catalyst for methanation and preparation method thereof | |
| CN103706373A (en) | Low-temperature high-activity methanation catalyst and preparation method thereof | |
| CN105413734B (en) | Nickel-based catalyst for preparing reducing gas by reforming methane-carbon dioxide and preparation method thereof | |
| CN106311242A (en) | Carbon dioxide methanation catalyst and preparation method thereof | |
| CN110639543A (en) | Methanation catalyst and preparation method thereof | |
| CN103706366B (en) | A kind of novel methanation catalyst and preparation method thereof | |
| CN103537288A (en) | Method for preparing methanation catalyst by adopting urea combustion method | |
| CN103801304B (en) | A kind of exempt to reduce slurry bed system methanation catalyst and method for making and application | |
| CN102921429A (en) | Coal-derived natural gas catalytic agent and preparation method thereof | |
| CN103846108A (en) | Preparation method of catalyst carrier for preparing substitute natural gas from coal-based syngas | |
| CN106563453A (en) | Composite catalyst for biomass gasification for preparing hydrogen-rich combustion gas, and preparation method thereof | |
| CN104815662A (en) | Low-temperature high-activity nano-composite catalyst for methanation of synthesis gas and preparation method thereof | |
| CN113318745A (en) | Preparation method of hydrogen-rich catalyst for biomass pyrolysis | |
| CN105080616A (en) | Preparation method of catalyst carrier through methanation of coke oven gas | |
| CN106064089B (en) | A kind of Regenrable catalyzed and preparation method thereof for catalyzing and reforming biologic oil hydrogen manufacturing | |
| CN110862873A (en) | Method for preparing hydrogenated biodiesel by catalyzing grease directional hydrodeoxygenation | |
| CN104479766B (en) | One kettle way prepares the novel method of algae green diesel | |
| CN105080591A (en) | Preparation method of catalyst through methanation of coke oven gas | |
| CN202543163U (en) | Device for preparing oxygen-containing liquid fuel by performing catalytic conversion on bio oil | |
| CN102389832B (en) | Catalyst for preparing C5 and C6 alkanes by hydrogenating high-activity sorbierite water phase, and preparation method of catalyst | |
| CN106179484B (en) | A kind of preparation method of carbon dioxide methanation catalyst | |
| CN105457622A (en) | Preparation method for Cox methanation catalyst carrier | |
| CN104513679A (en) | New technology for preparing natural gas through coke-oven gas methanation | |
| CN103801305B (en) | High capacity amount exempts from reduction slurry bed system methanation catalyst and method for making and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
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. |