CN1312350A - Coarse iron oxide desulfurizer for high temperature gas and its prepn - Google Patents
Coarse iron oxide desulfurizer for high temperature gas and its prepn Download PDFInfo
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- CN1312350A CN1312350A CN 01111031 CN01111031A CN1312350A CN 1312350 A CN1312350 A CN 1312350A CN 01111031 CN01111031 CN 01111031 CN 01111031 A CN01111031 A CN 01111031A CN 1312350 A CN1312350 A CN 1312350A
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Abstract
The desulfurizing agent is comprised of (wt%) 50-80% of red mud, 20-45% of binder and 3-10% of pore-forming agent, and its preparation method includes the following steps: grinding red mud, laminate compound with different silicon-aluminium ratio and pore-forming agent, uniformly mixing them, kneading them by adding water, extrusion moulding, drying and high temp. roasting so as to obtain the invented product with low cost, high strength, high fulfur valume and resistance to atomization. Said invention can be used in the fields of high temp. gas purification and desulfurizing purification of chemical raw material gas prepared by using coal, petroleum and natural gas as raw material.
Description
Coarse iron oxide desulfurizer for high temperature gas of the present invention and preparation belong to the sweetening agent preparation field, specifically relate to the high temperature coal gas purification agent in integrated gasification combined cycle for power generation and the fuel cell power generation technology and are the preparation method of desulfurizing decontaminating agent of the material gas of feedstock production with coal, oil, Sweet natural gas.
Coal is the abundantest in the world fossil fuel resource, with the coal is that the raw material generating is one of means of the most economical utilization of coal, and the coal gas steam combined cycle power generating (ICGG) of up-to-date emergence and fuel cell power generation technology will be coal cleaning, the efficient optimal path that utilizes.China is coal big country, and coal accounts for 76% of energy expenditure, and improving the pollution of coal utilization efficient and strictly controlled environment is an important subject that faces at present.The gas that gasification produces can produce H inevitably
2S, COS, CS
2(wherein more than 90% H
2S) HCN, NO
xWith components such as HCl.These component high temperature enter in the internal combustion turbine, can corrode blade, reduce the internal combustion turbine life-span, and discharging gas also can serious environment pollution.Therefore, to H in the coal gas
2S, COS, NO
xJust seem very necessary etc. removing of component.This has just determined that the coal gas of high temperature desulfurization is one of gordian technique of IGCC.
Coal gas desulfurization can adopt wet method and dry method to carry out, though wet desulphurization technology maturation, but need carry out at normal temperatures, can waste the sensible heat in the coal gas, and the coal gas of high temperature dry cleaning is compared with wet method and not only can be saved heat-exchange equipment, save Waste Water Treatment, and can improve generating efficiency, increase output rating, reduction cost of electricity-generating, and sulfur recovery elasticity is big.Although it should be noted developed countries, fail industrialization so far to high temperature coal gas purification (desulfurization) the research history of existing two more than ten years.In a few cover IGCC demo-plants that move in the world, still continuing to use wet desulphurization at present, trace it to its cause, is not the desulfuration efficiency and the Sulfur capacity height of sweetening agent, but the pulverizing problem in the use of above-mentioned sweetening agent high temperature.This has had a strong impact on the regeneration of sweetening agent, also can cause the loss of sweetening agent and the increase of coal gas particle concentration, is that the desulfurization of restriction coal gas of high temperature realizes one of biggest obstacle of steady running and through engineering approaches.In addition, ferrotitanium system or iron zinc fimily desulfurizing agent that developed countries adopts mostly cost an arm and a leg.Therefore, no matter still consider, all demand developing low price, high Sulfur capacity, the high-intensity desulfurizing agent for high-temp gas that is fit to China's national situation urgently from national conditions from technology.At the inevitable sweetening agent pulverizing problem that exists in the present coal gas of high temperature desulfurization and for many years Institutes Of Technology Of Taiyuan proposed the desulfurization route in the abundant theory of accumulation aspect the desulfurization research and industrialization practical experience and carried out in two steps, promptly slightly take off and add the inventive concept that essence is taken off.
The purpose of thick sweetening agent of coal gas of high temperature of the present invention and preparation is effectively to overcome the easy atomizing defective that aforementioned sweetening agent exists, and improves intensity of desulfurizer and Sulfur capacity, thus provide a kind of cheap, intensity is high, anti-efflorescence.The thick sweetening agent of the simple coal gas of high temperature of preparation method.It is characterized in that with steel mill's waste material red mud be main raw material, " imprison " theory and method according to professor's Li Chunhu proposition, the lamellar compound that adds the Different Silicon aluminum ratio is as binding agent, add pore-forming material again, make cylinder shape (φ 3-5mm) sweetening agent through steps such as grinding, mixing, extrusion, oven dry, high-temperature roastings.
Coarse iron oxide desulfurizer for high temperature gas of the present invention is characterized in that being is main raw material with steel mill's waste material red mud, adds the lamellar compound and the pore-forming material of Different Silicon aluminum ratio and forms, and its main active ingredient is Fe in the red mud
2O
3, its Fe
2O
3Content is 40-60 (wt) %, SiO
220-30 (wt) %, Al
2O
33-15%, all the other are the calcium oxide and the composition such as magnesium oxide of trace.
The preparation method of aforesaid coarse iron oxide desulfurizer for high temperature gas, it is characterized in that being: at first be that 50-80 (wt) % red mud was dried 3-8 hour under 60-90 ℃ of temperature, with the pore-forming material of the bonding agent of 20-45 (wt) %, 3-10 (wt) % through grind, mixing fully, adding suitable quantity of water mediates, placed 3-8 hour, make cylinder shape (φ 3-5mm) sweetening agent with banded extruder, natural air drying 2-3 days, or room temperature to 100 ℃ following the oven dry 5-8 hour, put into retort furnace 500-800 ℃ then and calcined 2-4 hour down.Make through quenching or naturally cooling more at last.
The preparation method of aforesaid coarse iron oxide desulfurizer for high temperature gas, it is characterized in that being: described bonding agent is the lamellar compound that wilkinite, kaolin, diatomite, refractory mortar or casting mold soil etc. contain the Different Silicon aluminum ratio, and described pore-forming material is xylogen, starch, carboxymethyl cellulose etc.
The activity rating of sweetening agent is to carry out in fixed-bed quartz reactor, 20 millimeters of reactor inside diameter, and sweetening agent is the right cylindrical of φ 3-5 millimeter, 500 ℃ of bed temperature of reaction, air speed 2000 hours
-1, reactant gases consists of H
243%, CO
213%, CO 30%, N
214%, import concentration of hydrogen sulfide 2-4g/M
3, before unstripped gas enters reactor, through the saturation water of 50 ℃ on water-bath band.When the desulfuration efficiency of sweetening agent is reduced to 70%, think promptly to penetrate that stop desulfurization, the question response device is cooled to about 400 ℃, logical oxygen and water vapour are regenerated to the sweetening agent after vulcanizing, to reach the purpose that recycles.
Coarse iron oxide desulfurizer for high temperature gas of the present invention is used for the high temperature coal gas purification of integrated gasification combined cycle for power generation and fuel cell power generation technology and is the desulfurizing and purifying of the material gas of feedstock production with coal, oil, Sweet natural gas, have cheap, intensity is high, Sulfur capacity is high, anti-efflorescence and the simple advantage of preparation method.
Describe the present invention in detail with table and embodiment below.
Embodiment one: take by weighing 700g kaolin, diatomite, refractory mortar, casting mold soil respectively, each and the red mud of 250g, the starch mixing of 50g, after adding the water kneading, placed 5 hours, moulding on banded extruder is afterwards made the bar shaped sweetening agent of 3 millimeters of φ, after air-dry 3 days, in retort furnace, calcined 3 hours for 800 ℃, promptly obtain the thick sweetening agent of coal gas of high temperature.Several sweetening agents five round-robin Sulfur capacity and Strength Changes in fixed-bed reactor see Table 1.Five times circulation back sweetening agent is not seen obvious efflorescence, and intensity is higher than fresh sweetening agent.
Five total Sulfur capacity that circulate of several different components sweetening agents of table 1
Embodiment two:
| The sweetening agent sequence number | Component | Vulcanize total Sulfur capacity (%) for five times | Fresh sample intensity (N/cm) | Five circulation back intensity (N/cm) |
| ????1# | Red mud+kaolin+starch | ????45 | ????154.97 | ????277.4 |
| ????2# | Red mud+diatomite+starch | ????80 | ????58.03 | ????132.9 |
| ????3# | Red mud+refractory mortar+starch | ????95 | ????126.80 | ????374.7 |
| ????4# | Red mud+casting mold soil+starch | ????60 | ????117.58 | ????400.3 |
According to the prescription of 2# in the table 1, produce 3 liters of sweetening agents, be used for the preceding factory's effluent coal gas of high temperature desulfurization of fertilizer plant's conversion section.Test-reactor is by the nickel chromium stainless steel pipe manufacturer of φ 108 * 6mm, length 2000mm, about 530 ℃ of desulfurization temperatures, air speed 3000h
-1, the used coal gas of desulfurization test is coal gas before nitrogen fertilizer plant's conversion, pressure 8kgf/cm
2, its average group becomes: CO27.3%, H
243.3%, CO
29.0%, N
219.9%, O
20.5%, H
2S concentration maintains 2000mg/m
3About, the water that hybrid reaction gas and water measurement pump are got gives vaporization in the hot device at coal gas, mix after, from the reactor reactor that enters into suitable for reading.
During regeneration, after the spinner-type flowmeter metering, the water of getting with regeneration water measurement pump mixes in the regeneration preheater after vaporization in water vaporizer by the air of air compressor outlet, is entered by the lower end of reactor.
After desulfurization finishes, earlier bed is carried out nature and be cooled to about 450 ℃, feed resurgent gases again and regenerate resurgent gases O
2Content 2-3%, H
2O (g) 95%, its H of regenerative process conveying end gasometry
2S concentration is lower than 20mg/m until both concentration
3The time, prove its regeneration fully, close the resurgent gases cooling after, feed desulphurization reaction gas and carry out next loop test.
The curing time and the sulfur capacity of factory's fixed bed lateral flow assay sweetening agent see Table 2.
Sulfur capacity does not take place to change significantly, and proceeds to active obvious decay is not found in the 16th sulfuration when stopping phenomenon, shows the sweetening agent stable performance, can be used for industrialized high temperature desulfurizing process.
The thick sweetening agent sulfuration/regeneration test result of table 2
| Cycle index curing time (h) recovery time (h) sulfur capacity (wt%) |
| ????1?????????42???????????18.0??????????25.19 ????2?????????19???????????19.0??????????10.45 ????3?????????32???????????19.5??????????17.72 ????4?????????28???????????20.0??????????15.00 ????5?????????28???????????24.0??????????16.5 ????6?????????33???????????15.0??????????23.16 ????7?????????24???????????17.0??????????18.2 ????8?????????24???????????24.0??????????12.63 ????9?????????27???????????15.0??????????12.23 ???10?????????26???????????18.0??????????26.33 ???11?????????25???????????13.5??????????17.17 ???12?????????30???????????13.5??????????21.79 ???13?????????31???????????14.0??????????19.27 ???14?????????36???????????13.0??????????19.94 ???15?????????36.5?????????12.0??????????23.04 ???16?????????29.5?????????12.0??????????21.87 |
| Accumulative total 471 267.5 300.49 |
Cure conditions: temperature 520-550 ℃, pressure 8kgf/cm
2, air speed 3000hr
-1,
H
2S inlet concentration 2000-3000mg/m
3
Regeneration condition: temperature 500-800 ℃, the pressure normal pressure
Claims (3)
1, a kind of coarse iron oxide desulfurizer for high temperature gas is characterized in that being is main raw material with steel mill's waste material red mud, adds the lamellar compound and the pore-forming material of Different Silicon aluminum ratio and forms, and its main active ingredient is Fe in the red mud
2O
3, its Fe
2O
3Content is 40-60 (wt) %, SiO
220-30 (wt) %, Al
2O
3-15%, all the other are calcium oxide, magnesium oxide and the titanium oxide of trace.
2, preparation method according to the described coarse iron oxide desulfurizer for high temperature gas of claim 1, it is characterized in that being: at first be that 50-80 (wt) % red mud was dried 3-8 hour under 60-90 ℃ of temperature, bonding agent with 20-45 (wt) %, the pore-forming material of 3-10 (wt) % is through grinding, complete mixing, adding suitable quantity of water mediates, placed 3-8 hour, make cylinder shape (φ 3-5mm) sweetening agent with banded extruder, natural air drying 2-3 days, or room temperature to 100 ℃ following the oven dry 5-8 hour, put into retort furnace 500-800 ℃ then and calcined 2-4 hour down, make through quenching or naturally cooling more at last.
3. according to the preparation method of the described coarse iron oxide desulfurizer for high temperature gas of claim 2, it is characterized in that being: described bonding agent is the lamellar compound that wilkinite, kaolin, diatomite, refractory mortar or casting mold soil etc. contain the Different Silicon aluminum ratio, and described pore-forming material is xylogen, starch, carboxymethyl cellulose.
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|---|---|---|---|
| CNB011110317A CN1133731C (en) | 2001-03-24 | 2001-03-24 | Coarse iron oxide desulfurizer for high temperature gas and its prepn |
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|---|---|---|---|
| CNB011110317A CN1133731C (en) | 2001-03-24 | 2001-03-24 | Coarse iron oxide desulfurizer for high temperature gas and its prepn |
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|---|---|
| CN1312350A true CN1312350A (en) | 2001-09-12 |
| CN1133731C CN1133731C (en) | 2004-01-07 |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195778B (en) * | 2008-01-02 | 2010-06-02 | 西南石油大学 | Production method of natural gas fine purification desulphurizing agent |
| CN102260542A (en) * | 2011-06-21 | 2011-11-30 | 太原理工大学 | Preparation method of three-dimensional ordered macroporous ferric oxide desulfurizer |
| CN102424764A (en) * | 2011-10-13 | 2012-04-25 | 太原理工大学 | Preparation method of iron oxide desulfurizer having controllable textural properties |
| CN101475844B (en) * | 2009-01-20 | 2012-07-04 | 太原理工大学 | Preparation of high temperature gas desulfurizer |
| CN102764629A (en) * | 2012-08-17 | 2012-11-07 | 太原理工大学 | Method for preparing absorbing agent for medium-temperature gas desulfurization |
| CN101386785B (en) * | 2008-10-24 | 2012-11-14 | 中国科学院山西煤炭化学研究所 | Desulphurizer for high-sulphur coal coke making and preparation method and applications |
| CN103182238A (en) * | 2011-12-29 | 2013-07-03 | 北京三聚环保新材料股份有限公司 | Method for enhancing strength of ball-type desulfurizer |
| CN105233879A (en) * | 2015-09-21 | 2016-01-13 | 四川理工学院 | Composite desulfurizer carrier, and desulfurizer based on carrier and preparation method thereof |
| CN110917831A (en) * | 2019-12-13 | 2020-03-27 | 西安润川环保科技有限公司 | Coal-fired flue gas desulfurizer and preparation method thereof |
| CN111116224A (en) * | 2019-12-31 | 2020-05-08 | 南京环福新材料科技有限公司 | Desulfurizer using red mud waste residue as active raw material, and preparation method and application thereof |
| CN112705163A (en) * | 2020-12-22 | 2021-04-27 | 长沙工研院环保有限公司 | Multi-metal in-situ doped desulfurizer based on low-coalification-degree inferior coal and preparation method thereof |
| CN113786723A (en) * | 2021-09-17 | 2021-12-14 | 昆明理工大学 | Preparation method of desulfurizer for purifying low-concentration carbonyl sulfide |
| CN115501741A (en) * | 2022-08-30 | 2022-12-23 | 四川轻化工大学 | High-activity iron oxide desulfurizer based on modified carrier and preparation method and application thereof |
| CN115814762A (en) * | 2022-10-27 | 2023-03-21 | 北京予知环境工程有限公司 | Containing magnetic gamma-Fe 2 O 3 Desulfurizing agent, and preparation method and application thereof |
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2001
- 2001-03-24 CN CNB011110317A patent/CN1133731C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101195778B (en) * | 2008-01-02 | 2010-06-02 | 西南石油大学 | Production method of natural gas fine purification desulphurizing agent |
| CN101386785B (en) * | 2008-10-24 | 2012-11-14 | 中国科学院山西煤炭化学研究所 | Desulphurizer for high-sulphur coal coke making and preparation method and applications |
| CN101475844B (en) * | 2009-01-20 | 2012-07-04 | 太原理工大学 | Preparation of high temperature gas desulfurizer |
| CN102260542A (en) * | 2011-06-21 | 2011-11-30 | 太原理工大学 | Preparation method of three-dimensional ordered macroporous ferric oxide desulfurizer |
| CN102260542B (en) * | 2011-06-21 | 2013-05-22 | 太原理工大学 | Preparation method of three-dimensional ordered macroporous ferric oxide desulfurizer |
| CN102424764A (en) * | 2011-10-13 | 2012-04-25 | 太原理工大学 | Preparation method of iron oxide desulfurizer having controllable textural properties |
| CN102424764B (en) * | 2011-10-13 | 2013-06-05 | 太原理工大学 | Preparation method of iron oxide desulfurizer having controllable textural properties |
| CN103182238B (en) * | 2011-12-29 | 2015-04-08 | 北京三聚环保新材料股份有限公司 | Method for enhancing strength of ball-type desulfurizer |
| CN103182238A (en) * | 2011-12-29 | 2013-07-03 | 北京三聚环保新材料股份有限公司 | Method for enhancing strength of ball-type desulfurizer |
| CN102764629A (en) * | 2012-08-17 | 2012-11-07 | 太原理工大学 | Method for preparing absorbing agent for medium-temperature gas desulfurization |
| CN105233879A (en) * | 2015-09-21 | 2016-01-13 | 四川理工学院 | Composite desulfurizer carrier, and desulfurizer based on carrier and preparation method thereof |
| CN110917831A (en) * | 2019-12-13 | 2020-03-27 | 西安润川环保科技有限公司 | Coal-fired flue gas desulfurizer and preparation method thereof |
| CN111116224A (en) * | 2019-12-31 | 2020-05-08 | 南京环福新材料科技有限公司 | Desulfurizer using red mud waste residue as active raw material, and preparation method and application thereof |
| CN111116224B (en) * | 2019-12-31 | 2022-03-15 | 南京环福新材料科技有限公司 | Desulfurizer using red mud waste residue as active raw material, and preparation method and application thereof |
| CN112705163A (en) * | 2020-12-22 | 2021-04-27 | 长沙工研院环保有限公司 | Multi-metal in-situ doped desulfurizer based on low-coalification-degree inferior coal and preparation method thereof |
| CN113786723A (en) * | 2021-09-17 | 2021-12-14 | 昆明理工大学 | Preparation method of desulfurizer for purifying low-concentration carbonyl sulfide |
| CN115501741A (en) * | 2022-08-30 | 2022-12-23 | 四川轻化工大学 | High-activity iron oxide desulfurizer based on modified carrier and preparation method and application thereof |
| CN115501741B (en) * | 2022-08-30 | 2023-11-03 | 四川轻化工大学 | High-activity ferric oxide desulfurizing agent based on modified carrier, and preparation method and application thereof |
| CN115814762A (en) * | 2022-10-27 | 2023-03-21 | 北京予知环境工程有限公司 | Containing magnetic gamma-Fe 2 O 3 Desulfurizing agent, and preparation method and application thereof |
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|---|---|
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