CN102021047B - Manganese lanthanum high-temperature gas desulfurizer and preparation method thereof - Google Patents
Manganese lanthanum high-temperature gas desulfurizer and preparation method thereof Download PDFInfo
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- CN102021047B CN102021047B CN 201010616929 CN201010616929A CN102021047B CN 102021047 B CN102021047 B CN 102021047B CN 201010616929 CN201010616929 CN 201010616929 CN 201010616929 A CN201010616929 A CN 201010616929A CN 102021047 B CN102021047 B CN 102021047B
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Abstract
The invention relates to a manganese lanthanum high-temperature gas desulfurizer and a preparation method thereof. The desulfurizer comprises the following components in mass percentage: 65-75 percent of MnCO3 and 25-35 percent of La(NO3)3.6H2O; by taking 100 mass percent of the two components as the reference, 10 percent of high-alumina bauxite and 5 percent of pore-forming agent are added, and the pore-forming agent is starch or carbon black. The method comprises the following concrete steps of: in the mass percent, carrying out ballmilling on manganese carbonate, lanthanum nitrate hexahydrate, the high-alumina bauxite and the pore-forming agent until the components are completely even; drying for 4-6 hours at the temperature of 100 DEG C; then adding water which is 15-35 percent the weight of the mixture; evenly stirring; carrying out extrusion molding on the powder and airing; baking for 6 hours at the temperature of 100 DEG C; finally roasting for 13-17 hours at the temperature of 800-950 DEG C to obtain the manganese lanthanum high-temperature gas desulfurizer. The desulfurizer prepared by the invention has the characteristics of good high-temperature desulfuration performance, high penetration sulphur capacity, simple preparation process and the like.
Description
Technical field:
The present invention relates to a kind of desulfurizing agent for high-temp gas and preparation method, particularly a kind of manganese lanthanum desulfurizing agent for high-temp gas and preparation method thereof.Belong to gas desulfurizer fabricating technology field.
Background technology:
Coal is the abundantest in the world fossil fuel resource, account for 92% of world's fossil fuel storing amount, generating is one of means of the most economical utilization of coal take coal as raw material, and the integrated gasification combined cycle for power generation (IGCC) and the fuel cell technology for power generation that become now study hotspot are clean, the efficient optimal paths that utilizes of coal.China is in the world maximum coal production state and consumption of coal state, and consumption of coal accounts for nearly 1/4 of world's consumption of coal total amount.In national primary energy source total quantity consumed, consumption of coal accounts for 3/4.Simultaneously, China also is one of coke big country, and this has also caused and has annually had a large amount of coal gas and need in addition processing and utilizing.Therefore improve efficiency of energy utilization and environmental contamination reduction is the important subject that faces at present.Contain a large amount of sulfide in the gas after the gasification, such as H
2S, COS(wherein are H more than 90%
2S).At high temperature, stink damp is known from experience etching apparatus, and environment is caused disadvantageous effect.Therefore the high temperature desulfurizing key is to remove hydrogen sulfide.。
The purifying method of the coal gas of current industrial applications is that hydrogen sulfide is removed in low temperature or Normal Atmospheric Temperature Liquid washing.Although wet desulphurization is industrial applications, need coal gas of high temperature is down to normal temperature again except hydrogen sulfide, so not only can waste the total sensible heat of coal gas, also need increase heat-exchange equipment, this has just reduced the economic benefit of coal gas.Dry desulfurization is compared with wet desulphurization and is had the following advantages:
1) recyclable coal gas of high temperature always accounts for the sensible heat of calorific value about 15%～20%;
2) saved heat exchanger, reduced facility investment, reduced production costs;
3) the visual market requirement situation of desulfurizer regeneration product is produced sulfuration and sulfuric acid;
4) the coal-tar middle oil magazine that waits of coal gas can not cause line clogging because of condensation.
Therefore, the desulfurization of researching high-temperature coal gas dry-method is significant.
Two conduct in-depth research coal gas desulfurization during the last ten years both at home and abroad, developed a series of sweetening agent, but technical problem causes the coal gas of high temperature desulfurization to fail so far industrial applications because sweetening agent exists that the high temperature desulfurizing performance is not good, sulfidation poor stability, low, the easy efflorescence of desulfurization precision, breakthrough sulphur capacity are low etc.
Summary of the invention:
One of purpose of the present invention is to overcome problems of the prior art a kind of manganese lanthanum desulfurizing agent for high-temp gas is provided.
Two of purpose of the present invention is to provide the preparation method of this sweetening agent.
For achieving the above object, the present invention adopts following technical scheme:
A kind of manganese lanthanum desulfurizing agent for high-temp gas is characterized in that the composition of this sweetening agent and quality percentage composition are:
MnCO
3 65～75%， La(NO
3)
3·6H
2O
25～35%
Be benchmark by 100% of the mass percent of above-mentioned two compositions, other adds 10% alumine and 5% pore-forming material, and described pore-forming material is: any of starch and carbon black.
The preparation method of above-mentioned a kind of manganese lanthanum desulfurizing agent for high-temp gas, the detailed process and the step that it is characterized in that the method are: by above-mentioned mass percent, with manganous carbonate, lanthanum nitrate hexahydrate, alumine, pore-forming material through the ball mill ball milling fully evenly after, under 100 ℃ of temperature, dried 4～6 hours, then 15～35% the water that adds mixture quality, after stirring, with this powder extrusion molding, after drying, then under 100 ℃ of temperature, dried 6 hours, 800～950 ℃ of lower roastings 13～17 hours, namely obtain manganese lanthanum desulfurizing agent for high-temp gas at last.
The evaluation of sweetening agent of the present invention is carried out in fixed-bed quartz reactor, and the silica tube internal diameter is 15mm, and sweetening agent is Ф 2～4mm cylinder shape, and the bed temperature of reaction is 800 ℃, air speed 2000h
-1, the simulation composition of coal gas is: H
241.88%, CO
23.12%,
CO7.32%, import concentration of hydrogen sulfide are 3000ppm.When desulfuration efficiency is reduced to 85%, namely think to penetrate, stop desulfurization.
The sweetening agent of the present invention's preparation has overcome the not good problem of high temperature desulfurizing performance that exists in the prior art, and can improve sulfur capacity and the desulfurization precision of sweetening agent.Coal gas of high temperature manganese lanthanum sweetening agent of the present invention can be used for high temperature coal gas purification in integrated gasification combined cycle for power generation (IGCC) and the hydrogen production from coke oven gas technology and oil, Sweet natural gas is the desulfurizing and purifying of the material gas of raw material preparation, the advantage such as have that price is low, desulfurization precision is high, sulfur capacity is high and preparation technology is simple.
Embodiment
Below in conjunction with embodiment the present invention is described in detail.
Embodiment one
Take by weighing respectively the 25g lanthanum nitrate hexahydrate, 58.4g manganous carbonate, 8.34g alumine and 4.17g pore-forming material starch are after ball milling is even, be positioned over baking oven interior (100 ℃) oven dry 4～6 hours, 15～35% the water that adds again mixture quality, again its extrusion is become cylinder shape (Ф 2～4mm) sweetening agent base substrates, naturally dried 24 hours, and then put into 100 ℃ drying in oven 6 hours, put at last 900 ℃ of lower roastings of retort furnace 13～17 hours, namely obtain manganese lanthanum desulfurizing agent for high-temp gas.
The 1.5g sweetening agent that takes by weighing the aforesaid method preparation is positioned in the desulfurization evaluating apparatus, and the silica tube internal diameter of experiment usefulness is 15mm, and long is 1000mm.Curing temperature is 800 ℃, and air speed is 2000h
-1, pressure is 0.1MPa, and concentration of hydrogen sulfide is 3000ppm, and the coal gas average composition is H
241.88%, CO
23.12%, CO 7.32%, and all gas is all from steel cylinder gas, and remix behind mass flowmeter enters the fixed-bed reactor from the reactor upper end.
Under 800 ℃ high temperature, the sweetening agent curability of aforesaid method preparation and other serial sweetening agents relatively list in table 1.
Breakthrough sulphur capacity is the quality of the sweetening agent sulphur that per 100 gram sweetening agents absorb when penetrating, and by the experimental result of table 1 as can be known, manganese lanthanum sweetening agent has that resistance to chalking is strong, the desulfurization precision advantages of higher.
Embodiment two
Take by weighing respectively the 52.56g manganous carbonate, 22.5g lanthanum nitrate hexahydrate, 7.5g alumine and 3.75g pore-forming material carbon black, be made into powder, the Mn:La mol ratio is 9:1 in the powder, powder was positioned in the baking oven (100 ℃) oven dry after evenly 4～6 hours through ball milling, 15～35% the water that adds again mixture quality, again its extrusion is become cylinder shape (Ф 2～4mm) sweetening agent base substrates, naturally dried 24 hours, and then put into 100 ℃ drying in oven 6 hours, put at last retort furnace respectively at 850 ℃, 900 ℃, 950 ℃ of lower roastings 13～17 hours obtain A, B, three kinds of sweetening agents of C.
Experiment is got 1.5g and three kinds of sweetening agents of A, B, C of above-mentioned technique preparation are positioned over are carried out the desulfurization evaluation in the fixation reaction bed, and its desulfurization performance is as shown in table 2.
Drawn by above-mentioned experimental result: the sweetening agent of 900 ℃ of lower sintering has best desulfurization performance, and desulfuration efficiency is up to 99.9%, and time of break-through is 270min.
Claims (2)
1. manganese lanthanum desulfurizing agent for high-temp gas is characterized in that the composition of this sweetening agent and quality percentage composition are:
MnCO
3 65～75%， La(NO
3)
3·6H
2O
25～35%
Be benchmark by the mass percent 100% of above-mentioned two compositions, other adds 10% alumine and 5% pore-forming material, and described pore-forming material is: any in starch and the carbon black.
2. the preparation method of described a kind of manganese lanthanum desulfurizing agent for high-temp gas according to claim 1, the detailed process and the step that it is characterized in that the method are: by above-mentioned mass percent, with manganous carbonate, lanthanum nitrate hexahydrate, alumine, pore-forming material is after the ball mill ball milling is fully even, under 100 ℃ of temperature, dried 4～6 hours, then 15～35% the water that adds mixture quality, after stirring, with this powder extrusion molding, after drying, then under 100 ℃ of temperature, dried 6 hours, 800 ℃ of-950 ℃ of lower roastings 13～17 hours, namely obtain manganese lanthanum desulfurizing agent for high-temp gas at last.
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| CN102021047B true CN102021047B (en) | 2013-04-03 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029256A (en) * | 2007-03-16 | 2007-09-05 | 沈阳航空工业学院 | High-temperature semi-tar gas desulfurizer and its use |
| CN101519608A (en) * | 2009-02-24 | 2009-09-02 | 上海大学 | Manganese oxide based high-temperature coal gas desulfurizing agent and preparation method thereof |
Family Cites Families (1)
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| US20040178117A1 (en) * | 2003-03-11 | 2004-09-16 | Morton Robert W. | Desulfurization and novel compositions for same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029256A (en) * | 2007-03-16 | 2007-09-05 | 沈阳航空工业学院 | High-temperature semi-tar gas desulfurizer and its use |
| CN101519608A (en) * | 2009-02-24 | 2009-09-02 | 上海大学 | Manganese oxide based high-temperature coal gas desulfurizing agent and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 煤气高温脱硫的实验研究;鲍国杭等;《上海大学学报( 自然科学版)》;20080630;第14卷(第3期);299-305 * |
| 鲍国杭等.煤气高温脱硫的实验研究.《上海大学学报( 自然科学版)》.2008,第14卷(第3期),299-305. |
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