CN101455965B - Low steam-gas ratio transformation catalyst in hydrogen rich gas and preparation method thereof - Google Patents
Low steam-gas ratio transformation catalyst in hydrogen rich gas and preparation method thereof Download PDFInfo
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- CN101455965B CN101455965B CN2009100448163A CN200910044816A CN101455965B CN 101455965 B CN101455965 B CN 101455965B CN 2009100448163 A CN2009100448163 A CN 2009100448163A CN 200910044816 A CN200910044816 A CN 200910044816A CN 101455965 B CN101455965 B CN 101455965B
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Abstract
The invention relates to a CO shift catalyst for hydrogen-rich atmosphere and low gas-steam ratio conditions, and a preparation method thereof, which belongs to the technical field of water-coal-gas shift process and catalysts. The catalyst takes copper as an active component, and takes two, three or four selected from zinc, zirconium, rare earth elements or IIIA group elements as additives. The preparation method of the catalyst mainly adopts a coprecipitation method, wherein a metal salt solution is subjected to ultrasonic pretreatment to ensure more uniform components, and the catalyst is roasted at a temperature between 400 and 600 DEG C to obtain an ideal pore structure, so as to ensure that water vapor is easier to aggregate on the surface of the catalyst. The catalyst prepared by the method has the advantages of good active metal dispersibility, large specific surface area and the like, and also has high water-coal-gas shift activity under the conditions of rich hydrogen and low gas-steam ratio, and the CO conversion rate of the catalyst is more than 90 percent under the normal pressure and the conditions of a fixed bed reactor. The catalyst is a high-activity energy-savingwater-coal-gas shift catalyst which effectively eliminates CO in hydrogen-rich fuel gas under the condition of low gas-steam ratio.
Description
Technical field
The present invention relates to a kind of under low steam-gas ratio condition under the hydrogen rich gas atmosphere carbon monoxide transformation catalyst and preparation method thereof, belong to Water gas shift/WGS technology and catalyst technical field.
Background technology
In metallurgical process, produce a large amount of coke-stove gas, it is passed through the catalytic pyrolysis and the methane reforming reaction of tar successively, contain a large amount of H in the back gas of reforming
2, a spot of CO and CO
2, can be used as a kind of desirable hydrogen feedstock gas.Fuel cell is with its cleaning, characteristics of high efficiency, make it become a kind of novel Hydrogen Energy and utilize approach, but, in use, a spot of CO will cause fuel-cell catalyst Pt electrode to be poisoned, therefore the hydrogen-rich gas that makes of coke-stove gas must be removed CO in the unstripped gas before use, improves the output of H2 when Water gas shift/WGS can realize removing CO, is subjected to people's extensive attention.Wherein, the addition that increases water vapour helps promoting the activity of water gas converting catalyst, but must reduce water vapour consumption as far as possible for energy-conservation in the Water gas shift/WGS hydrogen manufacturing de-carbon now, when the transformation catalyst of commercial Application is operated under low steam-gas ratio, activity is subjected to great inhibition, H when CO content is higher in the feasible final back gas of reforming
2The underproduction, therefore developing efficient, energy-conservation, cheap, long-life low steam-gas ratio water gas converting catalyst has become the emphasis problem that various countries press for solution.
For adapting to energy-conservation hydrogen manufacturing requirement, a series of low steam-gas ratio catalyst have been developed abroad.LK-811, LK-821 and LK-142 as Toposoe company, the C18-7 of UCI company and C18-5, the ICI53-1 of ICI company, ICI83-2 and ICI83-3, the K3-111 of BASF AG etc., these catalyst can be kept higher CO conversion rate at steam-to-gas ratio less than 0.4 time.
The research of domestic low steam-gas ratio catalyst is very active in recent years, as L-1 type and B207 type, under the low steam-gas ratio condition (about～0.5), all has good benefit.
The article of one piece " rare-earth additive is to catalyst for low temperature shift reaction with low steam to carbon ratio Effect on Performance " that " chemical industry and engineering " (2006 the 27th the 6th phases of volume) delivers, point out under the low steam-gas ratio condition, add the effect that rare earth element may play the enrichment water vapour at catalyst surface, keep higher shift activity.
Summary of the invention
The purpose of this invention is to provide carbon monoxide transformation catalyst and preparation method thereof under a kind of low steam-gas ratio condition in hydrogen-rich gas.
The objective of the invention is to realize by following technological means.
Low steam-gas ratio transformation catalyst under a kind of hydrogen rich gas atmosphere, it is characterized in that having following composition and percentage by weight: cupric oxide is 10%～50%, two kinds of oxides in zinc oxide, zirconia, rare earth oxide, the IIIA family element oxide, or three kinds of oxides, or four kinds of oxides are 50%～90%;
Described cupric oxide, zinc oxide or zirconia are by a kind of the obtaining in nitrate, acetate, sulfate or the chloride; Described rare earth oxide is La
2O
3, CeO
2Or Nd
2O
5In a kind of; Described IIIA family element oxide is B
2O
3, Al
2O
3Or In
2O
3In a kind of.
The preparation method of low steam-gas ratio transformation catalyst under a kind of hydrogen rich gas atmosphere is characterized in that having following technical process and step:
A. with the deionized water solvent, by weight percentage, by cupric oxide is 10%～50%, two kinds of oxides in zinc oxide, zirconia, rare earth oxide, the IIIA family element oxide, or three kinds of oxides, or four kinds of oxides are 50%～90% to prepare two kinds, three kinds or four kinds of salting liquids in copper salt solution and rare earth, IIIA family element, zinc and the zirconium, mixed solution is carried out the ultrasonic wave homogenising handled 30～60 minutes;
B. above-mentioned mixed solution and precipitating reagent are progressively splashed in 60～80 ℃ of deionized waters that constantly stir simultaneously, be 7～9 with sodium hydroxide solution regulator solution pH value subsequently, stir ageing 1～3 hour, in 60～80 ℃ of thermostats, wore out 10～24 hours then, obtain precipitation;
C. with above-mentioned sedimentation and filtration, and spend deionised water 3～5 times, then 80～110 ℃ of dryings 10～20 hours;
D. with step c gained mixture 400～600 ℃ of following roastings 2～4 hours, obtain the mixed-metal oxides solid, then solid is ground into powder, extrusion modling in mould under 50～100MPa pressure, subsequently again through pulverizing, sieving, obtaining particle diameter is 20～40 purpose particles, is final catalyst.
Described ultrasonic wave homogenising treatment conditions: frequency is 42 ± 3 KHzs, and radio frequency power output is 85～140 watts, and heating power is 185 watts.
Described precipitating reagent is: one or both in sodium carbonate liquor, sodium hydroxide solution, urea, ammoniacal liquor or the ammonium hydrogencarbonate.
The catalyst that the inventive method makes detects by XRD and is oxide, and at the hydrogen rich gas atmosphere, under the low steam-gas ratio condition, it is higher to have the Water gas shift/WGS activity, energy-conservation, and technology is simple, raw material is cheap and advantage of low manufacturing cost.
In normal pressure, fixed bed reactors, 180～240 ℃ of reaction temperatures, steam-to-gas ratio 0.3～0.5, gas reaction air speed 0.5～1.0 * 10
4h
-1, reaction gas volume percentage H
265%～80%CO, 5%～10%CO
2Under 15%～25% condition, the carbon monoxide conversion ratio is greater than 90% in the hydrogen-rich combustion gas.
The catalyst that the inventive method is prepared into is a kind of under the prerequisite that consumes less water vapour, can effectively remove the energy-saving water gas conversion catalyst of carbon monoxide in the strong hydrogen rich gas combustion gas.
Description of drawings
Fig. 1 is that the embodiment of the invention one is an active component with copper, and neodymium, zinc and IIIA family element aluminum are the X-ray diffractogram (XRD) of the catalyst of auxiliary agent.
Fig. 2 is that the embodiment of the invention one is an active component with copper, neodymium, zinc and IIIA family element aluminum be the catalyst of auxiliary agent under steam-to-gas ratio 0.3 condition, gas composition changes block diagram before and after the experiment.
The specific embodiment
The present invention is further described below by embodiment, but method of the present invention is not limited in embodiment.
Embodiment 1: take by weighing 40g Cu (NO respectively
3)
23H
2O, 10g Nd (NO
3)
3.6H
2O, 24g Al (NO
3)
39H
2O and 50g Zn (NO
3)
26H
2O is dissolved in the 500ml deionized water, behind the stirring 20min, puts into the ultrasonic processing of ultrasonic wave tank 30min, simultaneously, takes by weighing 60g Na
2CO
3In the 600ml deionized water, slowly heating, to dissolving fully, the co-precipitation in liquid at the bottom of 60 ℃ of constant temperature deionizations with metal salt solution and aqueous slkali adjusts to 9 with the 1MNaOH aqueous solution with the pH value, stirs ageing 1h, precipitated liquid is transferred in the thermostatic oil bath, 80 ℃ of constant temperature are handled 24h, with the gained sedimentation and filtration, wash 3 times with deionized water, and at 110 ℃ of dry 10h, at 400 ℃ of roasting temperature 2h, last gained solid is ground into powder, uses the mould of diameter as 1.5cm with the mixture of above-mentioned gained, under 100MPa after the extrusion modling, with its fragmentation, sieve, get the powder of 20～40 order scopes and make catalyst.
Embodiment 2: take by weighing 30g Cu (NO respectively
3)
23H
2O, 40gAl (NO
3)
39H
2O and 40g Ce (NO
3)
36H
2O is dissolved in the 500ml deionized water, behind the stirring 20min, puts into the ultrasonic processing of ultrasonic wave tank 60min, simultaneously, takes by weighing 30g Na
2CO
3With 10g NaOH in the 500ml deionized water, slowly heating, to dissolving fully, the co-precipitation in liquid at the bottom of 80 ℃ of constant temperature deionizations with metal salt solution and alkali lye adjusts to 7 with the 1MNaOH aqueous solution with the pH value, stirs ageing 3h, precipitated liquid is transferred in the thermostatic oil bath, 60 ℃ of constant temperature are handled 10h, with the gained sedimentation and filtration, wash 5 times with deionized water, and at 80 ℃ of dry 24h, at 500 ℃ of roasting temperature 2h, last gained solid is ground into powder, uses the mould of diameter as 1.5cm with the mixture of above-mentioned gained, under 100MPa after the extrusion modling, with its fragmentation, sieve, get the powder of 20～40 order scopes and make catalyst.
Embodiment 3: take by weighing 40g Cu (NO respectively
3)
23H
2O, 30g Zn (NO
3)
26H
2O and 34gAl (NO
3)
36H
2O is dissolved in the 500ml deionized water, behind the stirring 20min, puts into the ultrasonic processing of ultrasonic wave tank 30min, simultaneously, takes by weighing 42g NaHCO
3With 10g NaOH in the 500ml deionized water, slowly heating, to dissolving fully, the co-precipitation in liquid at the bottom of 80 ℃ of constant temperature deionizations with metal salt solution and alkali lye adjusts to 9 with the 1MNaOH aqueous solution with the pH value, stirs ageing 2h, precipitated liquid is transferred in the thermostatic oil bath, 60 ℃ of constant temperature are handled 24h, with the gained sedimentation and filtration, wash 4 times with deionized water, and at 100 ℃ of dry 16h, at 400 ℃ of roasting temperature 4h, last gained solid is ground into powder, uses the mould of diameter as 1.5cm with the mixture of above-mentioned gained, under 75MPa after the extrusion modling, with its fragmentation, sieve, the powder of getting 20～40 order scopes is a catalyst.
Embodiment 4: take by weighing 50g Cu (NO respectively
3)
23H
2O, 60g Zn (NO
3)
26H
2O and 34gZr (NO
3)
45H
2O is dissolved in the 500ml deionized water, behind the stirring 20min, puts into the ultrasonic processing of ultrasonic wave tank 40min, simultaneously, takes by weighing 45g NaHCO
3In the 500ml deionized water, slowly heating, to dissolving fully, the co-precipitation in liquid at the bottom of 70 ℃ of constant temperature deionizations with metal salt solution and aqueous slkali adjusts to 7 with the 1MNaOH aqueous solution with the pH value, stirs ageing 2h, precipitated liquid is transferred in the thermostatic oil bath, 70 ℃ of constant temperature are handled 24h, with the gained sedimentation and filtration, wash 4 times with deionized water, and at 110 ℃ of dry 16h, at 600 ℃ of roasting temperature 2h, last gained solid is ground into powder, uses the mould of diameter as 1.5cm with the mixture of above-mentioned gained, under 50MPa after the extrusion modling, with its fragmentation, sieve, get the powder of 20～40 order scopes and make catalyst.
The assessment experiment: the catalyst of getting in the embodiment of the invention 1 is assessed on micro-reaction equipment, 180～240 ℃ of reaction temperatures, and catalyst amount 1ml, reducing condition are 160 ℃ and 250 ℃ of difference reductase 12 h, reducing gas consists of 10%H
2/ N
2The reducing gas flow is 30ml/min.The composition of the rich H-H reaction gas of water-gas sees Table 1, gas volume air speed 0.6 * 10
-4h
-1, experimental result sees Table 2 under the physical parameter of this catalyst and the low steam-gas ratio, and Fig. 1 is the XRD figure spectrum of gained oxide after this complex catalyst precursor thing roasting, gas composition variation schematic diagram before and after experiment when Fig. 2 is this catalyst reaction condition steam-to-gas ratio 0.3.
The rich hydrogen unstripped gas of table 1 Water gas shift/WGS is formed
| Form | H 2 | CO | CO 2 | CH 4 |
| Volumn concentration, % | 75.3 | 5.4 | 17.8 | 1.5 |
Table 2 catalyst physical parameter and CO conversion ratio
Claims (3)
1. the preparation method of low steam-gas ratio transformation catalyst under the hydrogen rich gas atmosphere is characterized in that having following technical process and step:
A. with the deionized water solvent, by weight percentage, by cupric oxide is 10%～50%, two kinds of oxides in zinc oxide, zirconia, rare earth oxide, the IIIA family element oxide, or three kinds of oxides, or four kinds of oxides are 50%～90% to prepare two kinds, three kinds or four kinds of salting liquids in copper salt solution and rare earth, IIIA family element, zinc and the zirconium, mixed solution is carried out the ultrasonic wave homogenising handled 30～60 minutes;
B. above-mentioned mixed solution and precipitating reagent are progressively splashed in 60～80 ℃ of deionized waters that constantly stir simultaneously, be 7～9 with sodium hydroxide solution regulator solution pH value subsequently, stir ageing 1～3 hour, in 60～80 ℃ of thermostats, wore out 10～24 hours then, obtain precipitation;
C. with above-mentioned sedimentation and filtration, and spend deionised water 3～5 times, then 80～110 ℃ of dryings 10～20 hours;
D. with step c gained mixture 400～600 ℃ of following roastings 2～4 hours, obtain the mixed-metal oxides solid, then solid is ground into powder, extrusion modling in mould under 50～100MPa pressure, subsequently again through pulverizing, sieving, obtaining particle diameter is 20～40 purpose particles, is final catalyst.
2. the preparation method of low steam-gas ratio transformation catalyst under the hydrogen rich gas atmosphere as claimed in claim 1, it is characterized in that described ultrasonic wave homogenising treatment conditions: frequency is 42 ± 3 KHzs, and radio frequency power output is 85～140 watts, and heating power is 185 watts.
3. the preparation method of low steam-gas ratio transformation catalyst under the hydrogen rich gas atmosphere as claimed in claim 1 is characterized in that described precipitating reagent is: one or both in sodium carbonate liquor, sodium hydroxide solution, urea, ammoniacal liquor or the ammonium hydrogencarbonate.
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| CN102091617B (en) * | 2010-12-21 | 2012-07-25 | 福州大学 | Cu-based low-temperature water gas conversion catalyst under hydrogen rich reformed gas and preparation method thereof |
| CN102698783A (en) * | 2012-05-30 | 2012-10-03 | 大连理工大学 | Method for preparing metal-modified alpha type molybdenum carbide catalyst and application of metal-modified alpha type molybdenum carbide catalyst in low-temperature water-gas shift reaction |
| CN103170339B (en) * | 2013-01-22 | 2016-10-05 | 中国科学院过程工程研究所 | Cu base high-temperature water gas conversion catalyst and preparation method thereof in a kind of hydrogen-rich atmosphere |
| CN104511281A (en) * | 2013-09-27 | 2015-04-15 | 中国石油天然气股份有限公司 | Water gas wide temperature shift catalyst, preparation and application thereof |
| CN113083312B (en) * | 2019-12-23 | 2023-11-17 | 中石化南京化工研究院有限公司 | Carbon monoxide conversion catalyst and preparation method thereof |
| CN115920909A (en) * | 2022-12-21 | 2023-04-07 | 浙江大学衢州研究院 | xCuO-yIn for CO selective oxidation in hydrogen-rich gas 2 O 3 /CeO 2 Catalyst and preparation method thereof |
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Effective date of registration: 20140520 Address after: 226600 Haian County in Jiangsu province north of the city of Nantong City Industrial Zone (Da Gong Zhen Ben Ji Cun, 31 group) Patentee after: Nantong Rong Lida Aluminum Co. Ltd. Address before: 200444 Baoshan District Road, Shanghai, No. 99 Patentee before: Shanghai University |