CN101735862B - Preparation method of modified semicoke high temperature coal gas desulfurizer - Google Patents
Preparation method of modified semicoke high temperature coal gas desulfurizer Download PDFInfo
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- CN101735862B CN101735862B CN200910227869A CN200910227869A CN101735862B CN 101735862 B CN101735862 B CN 101735862B CN 200910227869 A CN200910227869 A CN 200910227869A CN 200910227869 A CN200910227869 A CN 200910227869A CN 101735862 B CN101735862 B CN 101735862B
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Abstract
The invention discloses a preparation method of modified semicoke high temperature coal gas desulfurizer, belonging to the technical field of coal chemical industry and preparation and application of desulfurizer. The technology method is characterized in that nonideal weakly caking coal semicoke in Yulin in Shaanxi Province with smaller original specific surface area and pore volume is activated, taking semicoke for improving surface pore structure and property as carrier of the desulfurizer, coprecipitating through ultrasonic wave to obtain the desulfurizer with high sulfur capacity, high desulfuration efficiency and high desulfuration precision, the selected carrier semicoke has low price and can be an ideal carrier through modification; the main active component zinc ferrite has higher sulfur capacity and desulfuration activity; ultrasonic wave can be utilized to effectively improve the dispersion degree of active components on the carrier in the preparation technology to increase the contact area of active components and gas H2S; and different assistants such as cerium oxide and manganese oxide are added to improve desulfuration activity and desulfuration efficiency of the desulfurizer.
Description
Technical field
The preparation method of modified semicoke high temperature coal gas desulfurizer of the present invention belongs to the technical field of the preparation and the application of Coal Chemical Industry and sweetening agent, specifically relates to a kind of technical field of preparation and gas sweetening of modified semicoke high temperature coal gas desulfurizer.
Background technology
Desulfurizing agent for high-temp gas development in future trend is compound and the load metal oxide sweetening agent.At present, the complex metal oxides sweetening agent originally can not satisfy the requirement that large-scale industrialization is used in the aspects such as mechanical strength, regeneration and economy of desulfurization precision, Sulfur capacity, sweetening agent.In MOX, add carbon material, silicon, al oxide, gac, the load metal oxide sweetening agent of auxiliary agents such as brick and tile soil and kaolin all has improvement preferably at aspects such as desulfuration efficiency, mechanical strength, Sulfur capacity and regeneration.Therefore, auxiliary agents such as carrier, additive choose and the preparation technology of sweetening agent can both produce bigger influence to the performance of sweetening agent, particularly important to the industrial application of sweetening agent.Carrier is the dispersing metal oxides active ingredient well, makes the active site fully combine with hydrogen sulfide, improves the transformation efficiency in active site a circulation to greatest extent.Moreover, like absorbent charcoal carrier, itself also have desulphurizing activatedly, this has improved effective Sulfur capacity of sweetening agent widely.Semicoke is coal (500 ℃-600 ℃) pyrolytic product under low temperature, and more hydrogen and oxygen are contained in inside, and more rich hole and surface tissue are arranged, so the chemical modification ratio is easier to, and price is comparatively cheap.Some regional Datong District, Shuozhou one band and provinces such as Guizhou, Shaanxi and the Inner Mongol like Shanxi in China are all containing a large amount of weak caking coals, and its resident's gas engineering adopts upright furnace gas making mostly, a large amount of semicokes of by-product.Pile up like a mountain for these semicokes, and serious environment pollution is said from clean coal technology and point of view of environment protection, utilizes cheap semicoke to be carrier, on semicoke, carries out middle high temperature desulfurizing metal oxide supported, is the sweetening agent carrier that development potentiality is arranged very much.It is the desulfurizing agent for high-temp gas of carrier with flyash that patent CNIO1235324A discloses a kind of.This sweetening agent has higher desulphurizing activated physical strength, and the flyash of power plant is utilized again, turns waste into wealth, and has opened up the new way of preparation sweetening agent.Consider from the preparation technology aspect how to make the sweetening agent hole flourishing, surface-area increases, thereby is easy to the hydrogen sulfide diffusion, and for hydrogen sulfide and active ingredient provide bigger attaching space, improving desulfuration efficiency as much as possible also is significant and consideration.Traditional mixing method, pickling process, the precipitator method, scorification all can't satisfy this requirement.In the preparation process of sweetening agent, use ultrasonic energy obviously to improve the performance of sweetening agent,, the desulfurizer activity center is uniformly dispersed, improve the activity of sweetening agent as increasing the surface-area of sweetening agent.Patent CN101126115A discloses a kind of preparation method of high-sulfur iron-containing series desulfurizing agent, makes Sulfur capacity 12.5%-25.1% of sweetening agent by the ultrasonic oscillation means.Patent CN1733611A discloses a kind of preparation method of Zirconium dioxide nano powder material, through the ultrasonic dispersing effect, and has investigated the influence of different capacity and time, the good product dispersibility that obtains, and intensity is high, good toughness.
Summary of the invention
The preparing method's of modified semicoke high temperature coal gas desulfurizer of the present invention purpose is to provide a kind of and utilizes cheap semicoke to be carrier, uses the ultrasonic dispersing effect, prepares the technical scheme of the method for the load-type desulfurizer that a kind of desulfuration efficiency is high, Sulfur capacity is high.
The preparation method of modified semicoke high temperature coal gas desulfurizer of the present invention; It is characterized in that it being that a kind of its original specific surface area and all smaller imperfect weakly caking coal semicoke of pore volume with the Yulin carries out activation; With the semicoke that improves its surface pore structure and character carrier as sweetening agent; Obtain the process method of the sweetening agent of a kind of high Sulfur capacity, high desulfurization efficiency and high desulfurization precision through the UW prepared by co-precipitation, concrete process step is:
I, with former semicoke activation modification
I. acid activation:
With its original specific surface area of 6-8 purpose Yulin with pore volume is all smaller, pore volume is 0.0426cm
3.g
-1, specific surface area is 44.60m
2.g
-1Imperfect weakly caking coal semicoke; Immersing temperature earlier is 60 ℃-80 ℃; Concentration is in the salpeter solution of 30%-50% 2-3 hour, and then immersing temperature again is 60 ℃-80 ℃, and concentration is in the hydrofluoric acid solution of 30%-50% 2-3 hour; Afterwards with till deionized water wash to pH＞6, in 100 ℃-110 ℃ oven drying 2-4 hour;
Ii. high-temperature vapor activation:
Semicoke after the i acid activation processing is put into 700 ℃ of-800 ℃ of high temperature process furnances fed 10%-15% water vapour reactivate 2-3 hour, subsequent use;
The preparation of II, metal salt solution
Select analytical pure zinc nitrate and analytical pure iron nitrate for use, take by weighing at 1: 2, be dissolved into saturated solution with deionized water according to the two stoichiometry mol ratio;
III, interpolation auxiliary agent
In Step II gained saturated solution, add MnO respectively
2Or CeO
2, the mass percent that add-on accounts for the sweetening agent total mass is 0.5%-2%;
IV, UW co-precipitation
The subsequent use modified semicoke of mixture that Step II I is made and step I preparation is 6 with duty ratio: 10-8: 10 mixed; Place ultrasonic wave field; 40 ℃-60 ℃ of refining temperatures, power 600-900W, 0.5-1.5 hour action time; Ultrasonic generator is the JXD-09 type that Beijing Jinxing Ultrasonic Equipment Technology Co., Ltd. produces; The 0.2-0.5ml tensio-active agent being splashed in this mixture, open UW, is that the ammoniacal liquor of 20%-30% splashes in the mixture and precipitates with one minute speed of 100 with concentration simultaneously;
V, make sweetening agent presoma zinc ferrite
The throw out that step IV is made boiled 0.5-1 hour, and ageing 5-7 hour, and with deionized water wash to 6＜pH＜8, suction filtration becomes pie, oven dry was 12-14 hour under 100 ℃-120 ℃ temperature, 500 ℃-700 ℃ roasting 2-3 hour;
VI, make the sweetening agent finished product
The CP kaolin that in the sweetening agent presoma that step V makes, adds mass percent and be 60-70% is as sticker, and the analytical pure Zulkovsky starch that adds mass percent simultaneously and be 5-10% is as pore-forming material, and the molecular formula of analytical pure Zulkovsky starch is (C
6H
10O
5)
n, molecular weight is (162.14)
n, add deionized water again and mix, extruded moulding, through 100 ℃-120 ℃ dry 12-14 hour, 500 ℃-700 ℃ calcinings promptly got product after 2-3 hour.
The appreciation condition of modified semicoke high temperature coal gas desulfurizer of the present invention is: desulfurization temperature 500-600 ℃, and air speed 2000
-1, the concentration of import hydrogen sulfide is at 2800ppm, and the composition percent by volume of reactant gases is: H
2-39%, CO-27%, CO
2-12%, H
2S-0.2-0.3%, N
2-balanced gas, H
2O-10%.
The activity rating index of sweetening agent:
1) sulfur capacity=sweetening agent absorbs sulphur quality/original sweetening agent quality * 100%.
2) physical strength: adopt ZQJ-II type intelligence granule strength trier that big connection intelligent experimental machine factory produces that the sweetening agent of moulding is carried out strength detection.
3) desulfuration efficiency=import and export H
2Poor/import the H of S concentration
2S concentration * 100%.
The preparing method's of modified semicoke high temperature coal gas desulfurizer of the present invention advantage is: selected carrier semicoke is cheap, can become the ideal carrier through modification; The main active component zinc ferrite self has higher sulfur capacity and desulphurizing activated; Use UW can effectively improve the dispersity of active ingredient on carrier among the preparation technology, to increase active ingredient and H
2The contact area of S gas; Through adding different auxiliary agent cerium oxide, manganese oxide, improved the desulphurizing activated and desulfuration efficiency of sweetening agent.
Embodiment
Embodiment 1
Sweetening agent preparation condition: with the former semicoke of 6-8 purpose; Immersing temperature earlier is 80 ℃; Concentration is in 45% the salpeter solution 2.5 hours, and then immersing temperature again is 75 ℃, and concentration is in 30% the hydrofluoric acid solution 2.5 hours; Afterwards with till deionized water wash to pH＞6, in 110 ℃ of oven dryings 4 hours; Semicoke after acid activation handled is put into 700 ℃ of high temperature process furnances and was fed 10% steam activation 2 hours; Select analytical pure zinc nitrate and analytical pure iron nitrate, take by weighing at 1: 2, be dissolved into saturated solution with deionized water according to the two stoichiometry mol ratio; The MnO of adding 0.5%
2Semicoke after mixture and the subsequent use modification is 6: 10 a mixed with duty ratio, and is placed in the ultrasonic wave field 40 ℃ of refining temperatures, power 600W, 0.5 hour action time; The 0.5ml tensio-active agent being splashed in this mixture, open UW, is that 26% ammoniacal liquor splashes in the mixture and precipitates with one minute speed of 100 with concentration simultaneously; Afterwards throw out was boiled 1 hour, ageing 6 hours, and with deionized water wash to 8＞pH＞6, suction filtration becomes pie, oven dry was 12 hours under 120 ℃ temperature, 500 ℃ of roastings 2 hours; Adding mass percent is that 60% kaolin, mass percent are 5% Zulkovsky starch, mix with deionized water, and extruded moulding, 120 ℃ of dryings of warp 12 hours, 500 ℃ of calcinings promptly got product 1 after 2 hours.
Sweetening agent appreciation condition: 500 ℃ of desulfurization temperatures, air speed 2000
-1
After product 1 once vulcanizes, Sulfur capacity 35.75%, physical strength 29.55N.m
-1, desulfuration efficiency 95.48%.
Embodiment 2
The sweetening agent preparation condition: the high-temperature vapor activation condition is: temperature is 750 ℃, 13% water vapour, activation 2.5 hours; The MnO of adding 1.5%
2Auxiliary agent; And with semicoke after the subsequent use modification be 7: 10 mixed with duty ratio; UW operating power 800W, 1 hour action time, 50 ℃ of water-baths; 600 ℃ of presoma calcining temperatures, calcination time 2.5 hours; Adding mass percent is that 65% kaolin, mass percent are 7% Zulkovsky starch, 600 ℃ of shaping desulfurizing agent calcining temperatures, and calcination time promptly got product 2 in 2.5 hours; Other step conditions are with embodiment 1.
Sweetening agent appreciation condition: 550 ℃ of desulfurization temperatures, air speed 2000
-1
After product 2 once vulcanizes, Sulfur capacity 43.02%, physical strength 32.99N.m
-1, desulfuration efficiency 98.97%.
Embodiment 3
The sweetening agent preparation condition: the high-temperature vapor activation condition is: temperature is 800 ℃, 15% water vapour, activation 3 hours; The MnO of adding 2%
2Auxiliary agent; And with semicoke after the subsequent use modification be 8: 10 mixed with duty ratio; UW operating power 900W, 1.5 hours action time, 60 ℃ of water-baths; 700 ℃ of presoma calcining temperatures, calcination time 3 hours; Adding mass percent is that 70% kaolin, mass percent are 10% Zulkovsky starch, 700 ℃ of shaping desulfurizing agent calcining temperatures, and calcination time promptly got product 3 in 3 hours; Other step conditions are with embodiment 1.
Sweetening agent appreciation condition: 600 ℃ of desulfurization temperatures, air speed 2000
-1
After product 3 once vulcanizes, Sulfur capacity 40.58%, physical strength 30.25N.m
-1, desulfuration efficiency 96.33%.
Embodiment 4
The sweetening agent preparation condition: the high-temperature vapor activation condition is: temperature is 700 ℃, 10% water vapour, activation 2 hours; The CeO of adding 0.5%
2Auxiliary agent; And with semicoke after the subsequent use modification be 6: 10 mixed with duty ratio; UW operating power 600W, 0.5 hour action time, 40 ℃ of water-baths; 500 ℃ of presoma calcining temperatures, calcination time 2 hours; Adding mass percent is that 60% kaolin, mass percent are 5% Zulkovsky starch, 500 ℃ of shaping desulfurizing agent calcining temperatures, and calcination time promptly got product 4 in 2 hours; Other step conditions are with embodiment 1.
Sweetening agent appreciation condition: 500 ℃ of desulfurization temperatures, air speed 2000
-1
After product 4 once vulcanizes, Sulfur capacity 38.72%, physical strength 29.50N.m
-1, desulfuration efficiency 97.33%.
Embodiment 5
The sweetening agent preparation condition: the high-temperature vapor activation condition is: temperature is 750 ℃, 13% water vapour, activation 2.5 hours; The CeO of adding 1.5%
2Auxiliary agent; And with semicoke after the subsequent use modification be 7: 10 mixed with duty ratio; UW operating power 800W, 1 hour action time, 50 ℃ of water-baths; 600 ℃ of presoma calcining temperatures, calcination time 2.5 hours; Adding mass percent is that 65% kaolin, mass percent are 7% Zulkovsky starch, 600 ℃ of shaping desulfurizing agent calcining temperatures, and calcination time promptly got product 5 in 2.5 hours; Other step conditions are with embodiment 1.
Sweetening agent appreciation condition: 550 ℃ of desulfurization temperatures, air speed 2000
-1
After product 5 once vulcanizes, Sulfur capacity 38.11%, physical strength 28.15N.m
-1, desulfuration efficiency 95.37%.
Embodiment 6
The sweetening agent preparation condition: the high-temperature vapor activation condition is: temperature is 800 ℃, 15% water vapour, activation 3 hours; The CeO of adding 2%
2Auxiliary agent; And with semicoke after the subsequent use modification be 8: 10 mixed with duty ratio; UW operating power 900W, 1.5 hours action time, 60 ℃ of water-baths; 700 ℃ of presoma calcining temperatures, calcination time 3 hours; Adding mass percent is that 70% kaolin, mass percent are 10% Zulkovsky starch, 700 ℃ of shaping desulfurizing agent calcining temperatures, and calcination time promptly got product 6 in 3 hours; Other step conditions are with embodiment 1.
Sweetening agent appreciation condition: 600 ℃ of desulfurization temperatures, air speed 2000
-1
After product 6 once vulcanizes, Sulfur capacity 30.85%, physical strength 30.22N.m
-1, desulfuration efficiency 97.08%.
Claims (1)
1. the preparation method of modified semicoke high temperature coal gas desulfurizer; It is characterized in that it being that a kind of its original specific surface area and all smaller imperfect weakly caking coal semicoke of pore volume with the Yulin carries out activation; With the semicoke that improves its surface pore structure and character carrier as sweetening agent; Obtain the process method of the sweetening agent of a kind of high Sulfur capacity, high desulfurization efficiency and high desulfurization precision through the UW prepared by co-precipitation, concrete process step is:
I, with former semicoke activation modification
I. acid activation:
With its original specific surface area of 6-8 purpose Yulin with pore volume is all smaller, pore volume is 0.0426cm
3.g
-1, specific surface area is 44.60m
2.g
-1Imperfect weakly caking coal semicoke; Immersing temperature earlier is 60 ℃-80 ℃; Concentration is in the salpeter solution of 30%-50% 2-3 hour, and then immersing temperature again is 60 ℃-80 ℃, and concentration is in the hydrofluoric acid solution of 30%-50% 2-3 hour; Afterwards with till deionized water wash to pH＞6, in 100 ℃-110 ℃ oven drying 2-4 hour;
Ii. high-temperature vapor activation:
Semicoke after the i acid activation processing is put into 700 ℃ of-800 ℃ of high temperature process furnances fed 10%-15% water vapour reactivate 2-3 hour, subsequent use;
The preparation of II, metal salt solution
Select analytical pure zinc nitrate and analytical pure iron nitrate for use, take by weighing at 1: 2, be dissolved into saturated solution with deionized water according to the two stoichiometry mol ratio;
III, interpolation auxiliary agent
In Step II gained saturated solution, add MnO respectively
2Or CeO
2, the mass percent that add-on accounts for the sweetening agent total mass is 0.5%-2%;
IV, UW co-precipitation
The subsequent use modified semicoke of mixture that Step II I is made and step I preparation is 6 with duty ratio: 10-8: 10 mixed; Place ultrasonic wave field; 40 ℃-60 ℃ of refining temperatures, power 600-900W, 0.5-1.5 hour action time; Ultrasonic generator is the JXD-09 type that Beijing Jinxing Ultrasonic Equipment Technology Co., Ltd. produces; The 0.2-0.5ml tensio-active agent being splashed in this mixture, open UW, is that the ammoniacal liquor of 20%-30% splashes in the mixture and precipitates with one minute speed of 100 with concentration simultaneously;
V, make sweetening agent presoma zinc ferrite
The throw out that step IV is made boiled 0.5-1 hour, and ageing 5-7 hour, and with deionized water wash to 6＜pH＜8, suction filtration becomes pie, oven dry was 12-14 hour under 100 ℃-120 ℃ temperature, 500 ℃-700 ℃ roasting 2-3 hour;
VI, make the sweetening agent finished product
The CP kaolin that in the sweetening agent presoma that step V makes, adds mass percent and be 60-70% is as sticker, and the analytical pure Zulkovsky starch that adds mass percent simultaneously and be 5-10% is as pore-forming material, and the molecular formula of analytical pure Zulkovsky starch is (C
6H
10O
5)
n, molecular weight is (162.14)
n, add deionized water again and mix, extruded moulding, through 100 ℃-120 ℃ dry 12-14 hour, 500 ℃-700 ℃ calcinings promptly got product after 2-3 hour.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103463963B (en) * | 2013-09-13 | 2015-06-24 | 中国科学院工程热物理研究所 | Load type zinc ferrite based desulfurizing agent and preparation method thereof |
| CN107583637A (en) * | 2017-10-26 | 2018-01-16 | 华北理工大学 | The sintering flue gas desulfurization agent of semicoke loading ZnO and its solvothermal preparation method |
| CN108435213A (en) * | 2018-05-10 | 2018-08-24 | 钦州学院 | Fly ash loading metal oxide catalyst of starch conversion and preparation method thereof |
| CN108558630A (en) * | 2018-05-10 | 2018-09-21 | 钦州学院 | The method that anthracene prepares anthraquinone |
| CN109399786A (en) * | 2018-09-29 | 2019-03-01 | 北京涌阔科技有限公司 | A kind of preparation method of micropore biological filtrate |
| CN110694614A (en) * | 2019-09-04 | 2020-01-17 | 重庆大学 | Preparation method of active semicoke carrier suitable for low-temperature SCR denitration catalyst |
| CN111359673A (en) * | 2020-03-26 | 2020-07-03 | 安徽元琛环保科技股份有限公司 | MnO2PPS composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1283669A (en) * | 2000-07-14 | 2001-02-14 | 太原理工大学 | Desulfurizing agent for high-temp gas and its preparing process |
| CN1970696A (en) * | 2006-11-16 | 2007-05-30 | 中国海洋大学 | Method for preparing active semicoking FCC gasoline and diesel oil adsorption desulfurizer |
| 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 |
-
2009
- 2009-12-18 CN CN200910227869A patent/CN101735862B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1283669A (en) * | 2000-07-14 | 2001-02-14 | 太原理工大学 | Desulfurizing agent for high-temp gas and its preparing process |
| CN1970696A (en) * | 2006-11-16 | 2007-05-30 | 中国海洋大学 | Method for preparing active semicoking FCC gasoline and diesel oil adsorption desulfurizer |
| 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 |
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