CN101450312A - Natural gas steam reforming catalyst and preparation method thereof - Google Patents
Natural gas steam reforming catalyst and preparation method thereof Download PDFInfo
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- CN101450312A CN101450312A CNA2007101909079A CN200710190907A CN101450312A CN 101450312 A CN101450312 A CN 101450312A CN A2007101909079 A CNA2007101909079 A CN A2007101909079A CN 200710190907 A CN200710190907 A CN 200710190907A CN 101450312 A CN101450312 A CN 101450312A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention belongs to the technical field of catalyst and relates to a natural gas steam reforming catalyst and a preparation method thereof. The catalyst takes alpha-alumina as a carrier, nickel oxide as an active ingredient, and lanthanum oxide, cerium oxide or neodymium oxide as a catalyst accelerator. The natural gas steam reforming catalyst is obtained by impregnating the alpha-alumina carrier into cerous nitrate (or lanthanum nitrate or neodymium nitrate) first before preparation, then drying and roasting to modify the carrier, impregnating the carrier into nickel nitrate, and drying and roasting the carrier. The catalyst prepared by the method is suitable to be used in lower water carbon ratio and can effectively prevent carbon deposition.
Description
Technical field:
The invention belongs to catalysis technical field, be specifically related to a kind of natural gas steam reforming catalyst and preparation method thereof, this catalyst is used for the technical process that natural gas and steam reaction are produced synthesis gas.
Background technology:
Natural gas is produced synthesis gas by steam-reforming, further synthetic ammonia, synthesizing methanol, produce the important approach that utilizes that hydrogen is natural gas.The natural gas steam reforming process need add excessive water vapour usually, with protection conversion of natural gas catalyst, to avoid the carbon distribution phenomenon, otherwise easy covering catalyst activated centre causes catalyst to pulverize adverse consequences such as blocking pipe.Factory is for energy-conservation, and factory adopts alap steam/hydrocarbons ratio operation usually.Low steam carbon ratio is finished drilling and is done reforming catalyst is had higher requirement, and needs reforming catalyst to have better anti-carbon performance.
Reforming catalyst is a Main Ingredients and Appearance with the aluminium oxide, and the acid site in the aluminium oxide is one of major reason that causes carbon distribution.In order to improve the anti-carbon performance of conversion of natural gas catalyst, can in the preparation of carrier, add alkaline assistant, as the disclosed method for preparing catalyst of patent of invention CN 85103556A: make the aluminiferous material of carrier and light rare earth compound becomes certain fineness earlier through ball milling powder, reshaping is the carrier of definite shape, and then be sintered to carrier with certain pore structure and intensity, then nickel salt solution and light rare earth compound immerse carrier together, soak good catalysis and resolve into last product through roasting.
Patent of invention CN 1176292A discloses a kind of steam reforming catalysts for lower hydrocarbons, with CaAl
2O
4(calcium aluminate) is carrier, and nickel-loaded or platinum bunch metal is an active constituent.CaO in the carrier of this catalyst must be fully with CaAl
2O
4Form exist, free CaO can not be arranged.
The preparation method of the disclosed a kind of rare earth hydrocarbon steam conversion catalyst of patent of invention CN 85100025A: aluminum nitrate, nickel nitrate, cerous nitrate, magnesia are put into sedimentation basin, mixed ammonium/alkali solutions with NaOH and sodium carbonate precipitates, and filtration washing is to there not being NO
3 -, do behaviour, and 500～600 ℃ of pre-calcination, pulverizing also adding graphite etc., the ring mould moulding with 16 * 16 * 5 again at 1000 ℃ of left and right sides calcination 4h, is used hydrogen reducing then, makes catalyst.
Summary of the invention:
The object of the invention is to provide a kind of conversion of natural gas catalyst that uses under lower steam/hydrocarbons ratio.
Catalyst of the present invention is a carrier with the Alpha-alumina, is active constituent with the nickel oxide, is co-catalyst with lanthana or cerium oxide or neodymia, is benchmark with the gross weight of catalyst, and it is formed percentage by weight and is: Al
2O
360%～80%, NiO 10%～20%, co-catalyst 1.0～10.0%.
Catalyst of the present invention prepares by following process: earlier alpha-alumina supports carried out modification and handles, and then the dipping nickel nitrate solution, and drying, roasting and get.
The present invention usually carries out the method that modification handles to alpha-alumina supports:: 1. alpha-alumina supports is immersed 0.5h～2h in cerous nitrate (or lanthanum nitrate, or the neodymium nitrate) solution, take out 100 ℃～140 ℃ oven dry down; 2. carrier is obtained the carrier of modification 600 ℃～1000 ℃ of roastings.
Alpha-alumina supports through modification is prepared into catalyst by the following method: 1. the alpha-alumina supports with modification immerses 0.5h～2h in the nickel nitrate solution, takes out 100 ℃～140 ℃ oven dry down, then 400 ℃～600 ℃ roastings; 2. repeating step 1. the NiO content in catalyst reach 10%～20%.
Among the present invention,, carrier is carried out modification handle: prepare α-Al according to conventional method earlier in order to improve the anti-carbon performance of catalyst
2O
3Carrier, the profile of carrier can be central columns, also can be five holes or seven apertures in the human head cylinder, can also be five muscle or seven muscle colyliforms; Then, this carrier is immersed in cerous nitrate (or lanthanum nitrate, or neodymium nitrate) solution,, obtain containing 1.0%～10.0% Ce again through super-dry, roasting
2O
3(or La
2O
3, or Rd
2O
3) carrier.Reduce the acidity of carrier surface by modification, helped improving the carbon accumulation resisting ability of carrier.
The catalyst of the inventive method preparation is adapted at using under the lower steam/hydrocarbons ratio.
The specific embodiment:
Below the present invention is further illustrated in conjunction with the embodiments:
Embodiment 1:
1. getting 10 profiles is the central column α-Al of Φ 16 * 16 * 8mm (external diameter is 16mm, and height is 16mm, and internal diameter is 8mm)
2O
3Carrier immerses 1h in the neodymium nitrate solution, takes out 120 ℃ of oven dry, 600 ℃～1000 ℃ roasting 2h～4h then, makes the Rd of load on the carrier
2O
3Content accounts for 4% of total weight of carrier after the modification; 2. carrier after the modification is immersed 0.5h～2h in the nickel nitrate solution, take out 100 ℃～140 ℃ oven dry down, again at 500 ℃～700 ℃ following roasting 2h～4h; 3. 2. repeating step so that the load capacity of NiO is 12%, obtains catalyst I.
Embodiment 2:
1. getting 10 profiles is the central column α-Al of Φ 16 * 16 * 8mm (external diameter is 16mm, and height is 16mm, and internal diameter is 8mm)
2O
3Carrier immerses 1h in the lanthanum nitrate hexahydrate, takes out 120 ℃ of oven dry, 600 ℃～1000 ℃ roasting 2h～4h then, makes the La of load on the carrier
2O
3Content accounts for 3% of total weight of carrier after the modification; 2. carrier after the modification is immersed 0.5h～2h in the nickel nitrate solution, take out 100 ℃～140 ℃ oven dry down, again at 500 ℃～700 ℃ following roasting 2h～4h; 3. 2. repeating step so that the load capacity of NiO is 12%, obtains catalyst I I.
Embodiment 3:
1. getting 10 profiles is the central column α-Al of Φ 16 * 16 * 8mm (external diameter is 16mm, and height is 16mm, and internal diameter is 8mm)
2O
3Carrier immerses 0.5h～2h in the nickel nitrate solution, takes out 100 ℃～140 ℃ oven dry down, again at 500 ℃～700 ℃ following roasting 2h～4h; 2. 1. repeating step so that the load capacity of NiO is 12%, obtains reference catalyst.
Embodiment 4:
Fill in respectively in the fixed bed reactors with above-mentioned catalyst and under low steam carbon ratio (steam/hydrocarbons ratio is 2.0) condition, to carry out the determination of activity of gas water steam reforming reaction.Reaction condition is: temperature is 800 ℃, and pressure is 3.0MPa, and air speed is 20000h
-1, steam/hydrocarbons ratio is 2.0.Measured catalyst activity is as follows:
| Sample | Relative activity, % |
| Catalyst I | 105 |
| Catalyst I I | 111 |
| Reference catalyst | 100 |
Claims (6)
1. a natural gas steam reforming catalyst is a carrier with the Alpha-alumina, is active constituent with the nickel oxide, is co-catalyst with lanthana or cerium oxide or neodymia, it is characterized in that the gross weight with catalyst is a benchmark, and it is formed percentage by weight and is: Al
2O
360%～80%, NiO 10%～20%, co-catalyst 1.0～10.0%.
2. according to the described Preparation of catalysts method of claim 1, it is characterized in that earlier alpha-alumina supports being carried out modification handles, and then the dipping nickel nitrate solution, and drying, roasting and get.
3. according to the described Preparation of catalysts method of claim 2, it is characterized in that the method for alpha-alumina supports being carried out the modification processing is: 1. alpha-alumina supports is immersed 0.5h～2h in the cerous nitrate solution, take out 100 ℃～140 ℃ oven dry down; 2. carrier is obtained the carrier of modification 600 ℃～1000 ℃ of roastings.
4. according to the described Preparation of catalysts method of claim 2, it is characterized in that the method for alpha-alumina supports being carried out the modification processing is: 1. alpha-alumina supports is immersed 0.5h～2h in the lanthanum nitrate hexahydrate, take out 120 ℃ of oven dry down; 2. carrier is obtained the carrier of modification 600 ℃～1000 ℃ of roastings.
5. according to the described Preparation of catalysts method of claim 2, it is characterized in that the method for alpha-alumina supports being carried out the modification processing is: 1. alpha-alumina supports is immersed 0.5h～2h in the neodymium nitrate solution, take out 120 ℃ of oven dry down; 2. carrier is obtained the carrier of modification 600 ℃～1000 ℃ of roastings.
6. according to the described Preparation of catalysts method of claim 2, it is characterized in that being prepared into catalyst by the following method through the alpha-alumina supports of modification: 1. the alpha-alumina supports with modification immerses 0.5h～2h in the nickel nitrate solution, taking-up is 120 ℃ of oven dry down, then 400 ℃～600 ℃ roastings; 2. repeating step 1. the NiO content in catalyst reach 10%～20%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101909079A CN101450312A (en) | 2007-11-29 | 2007-11-29 | Natural gas steam reforming catalyst and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101909079A CN101450312A (en) | 2007-11-29 | 2007-11-29 | Natural gas steam reforming catalyst and preparation method thereof |
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|---|---|
| CN101450312A true CN101450312A (en) | 2009-06-10 |
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ID=40732903
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102319574A (en) * | 2011-05-17 | 2012-01-18 | 太原理工大学 | Synthesis gas methanation catalyst and preparation thereof |
| CN102626628A (en) * | 2012-05-17 | 2012-08-08 | 太原理工大学 | Preparation method of synthetic gas methanation catalyst |
| CN103752320A (en) * | 2013-12-31 | 2014-04-30 | 南昌大学 | Mixed rare-earth modified methane steam reformed nickel-based catalyst and preparation method thereof |
| CN104383932A (en) * | 2014-09-26 | 2015-03-04 | 大连瑞克科技有限公司 | Preparation method for high stability catalyst through steam conversion of natural gas |
| CN105813737A (en) * | 2013-10-17 | 2016-07-27 | 巴西石油公司 | Catalyst for producing synthesis gas and method for producing same |
| CN111569893A (en) * | 2020-06-03 | 2020-08-25 | 西南化工研究设计院有限公司 | Low-cost natural gas conversion catalyst and preparation method thereof |
-
2007
- 2007-11-29 CN CNA2007101909079A patent/CN101450312A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102319574A (en) * | 2011-05-17 | 2012-01-18 | 太原理工大学 | Synthesis gas methanation catalyst and preparation thereof |
| CN102626628A (en) * | 2012-05-17 | 2012-08-08 | 太原理工大学 | Preparation method of synthetic gas methanation catalyst |
| CN105813737A (en) * | 2013-10-17 | 2016-07-27 | 巴西石油公司 | Catalyst for producing synthesis gas and method for producing same |
| CN103752320A (en) * | 2013-12-31 | 2014-04-30 | 南昌大学 | Mixed rare-earth modified methane steam reformed nickel-based catalyst and preparation method thereof |
| CN103752320B (en) * | 2013-12-31 | 2016-08-17 | 南昌大学 | Mischmetal modification methane vapor reforming nickel-base catalyst and preparation method thereof |
| CN104383932A (en) * | 2014-09-26 | 2015-03-04 | 大连瑞克科技有限公司 | Preparation method for high stability catalyst through steam conversion of natural gas |
| CN111569893A (en) * | 2020-06-03 | 2020-08-25 | 西南化工研究设计院有限公司 | Low-cost natural gas conversion catalyst and preparation method thereof |
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Open date: 20090610 |