CN102408923B - Hydrolysis method of COS in synthesis gas based on high-density circulating fluidization and gasification process - Google Patents
Hydrolysis method of COS in synthesis gas based on high-density circulating fluidization and gasification process Download PDFInfo
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- CN102408923B CN102408923B CN 201110306401 CN201110306401A CN102408923B CN 102408923 B CN102408923 B CN 102408923B CN 201110306401 CN201110306401 CN 201110306401 CN 201110306401 A CN201110306401 A CN 201110306401A CN 102408923 B CN102408923 B CN 102408923B
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Abstract
The invention provides a hydrolysis method of COS in a synthesis gas based on a high-density circulating fluidization and gasification process. In the hydrolysis method, aiming at the characteristics that the synthesis gas produced by an IGCC (integrated gasification combined cycle) power plant by adopting a whole coal gasification technology of a transportation bed reactor contains 17.0% by volume of H2O, 0.478% by volume of NH3 and 80-120ppm by volume of COS, a DJ-1A multifunctional purifying agent which is produced and developed by Hua Shuo science and technology Co., LTD is adopted, 80-120ppm by volume of COS in the synthesis gas is converted to H2S under the conditions that the temperature is 170-220 DEG C, the pressure is 2.7-3.3MPa and the space velocity is 1000-3000n<-1>, and the volume content of COS at the outlet is less than 10ppm, so as to meet the process requirement. The hydrolysis method of COS has the characteristics that CO+H2O=H2+CO2 shift side reaction is small under the condition of 17.0% by volume of H2O and simultaneously, the influences of impurities in the synthesis gas, such as NH3 and the like, are overcome.
Description
Technical field:
The present invention relates to coal gasification and integrated gasification combined cycle plants (IGCC) technical field, relate in particular to the method for hydrolysis of COS in a kind of typical synthesis gas that is applied to produce based on the ciculation fluidized coal gasifying process of high density.
Background technology:
The environmental issue that present China is brought based on the energy resource structure of coal has faced increasing international pressure, is badly in need of breakthrough and the innovation of clean coal technology.
China clean coal utilization technical office is a Rapid development stage, integrated gasification combined cycle plants (IGCC) generally believed in the world be with coal be converted into that electric energy is the most efficient, one of the mode of cleaning.
In the IGCC process, at first under uniform temperature and pressure condition, coal is converted into synthesis gas by gasification furnace, the synthesis gas that produces is through entering the gas turbine acting after the purified treatment, the high-temperature flue gas that gas turbine produces is by the feedwater of waste heat boiler heating boiler, produce superheated steam and continue to enter the steam turbine acting, realize the cascade utilization of energy.A typical IGCC power station comprises the gasification island, purifies island and Power island.
Wherein gasification furnace is the core component in the IGCC gasification island, and other are equipped with coal in the gasification island, coal supply, and devices such as ash discharge are its service.Technical process in the gasification furnace has determined coal gasification to produce the conditions such as component, temperature and pressure of synthesis gas.
The IGCC power plant of Dongguan electrification group construction has adopted world advanced person's the bed bioreactor integral coal gasification technology that transports (TRIG
TM), this project has been born development coal gas simultaneously and has been turned to basic Poly-generation demonstration project task.
TRIG
TMTechnology is advanced Coal Gasification Technology, has passed through the pilot-plant test that surpasses 40,000 hours, the TRIG that electrification group in Dongguan adopts
TMFor already disguising, the first Tianwan businessman in the world puts.Coal Gasification Technology can be divided into 3 classes at present, i.e. fixed bed, fluid bed and air flow bed.Wherein the fixed bed gasification technology is represented as normal pressure gas producer, lurgi pressure gasifier and BGL pressurized-gasification furnace (broken coal slag gasification furnace); Be represented as HTW gasification furnace, U-GAS gasification furnace and the ash of fluidized-bed gasification furnace melt poly-gasification furnace etc.; Airflow bed gasification furnace be represented as TEXACO gasification furnace, SHELL gasification furnace and GSP gasification furnace etc.TRIG
TMTechnology is difference and other Coal Gasification Technology obviously.Its characteristic is middle temperature operation (1000 ℃), adopts the ciculation fluidized mode of high density to carry out coal gasification course, and adopt the air gasification mode in the IGCC power station, has saved the air separation unit investment.
Adopt TRIG
TMIts typical operation temperature of technology gasification furnace is 920～1150 ℃, after vapor pressure scope 2.7～3.3MPa, the synthesis gas of generation are discharged by top of gasification furnace, enters and presses superheated steam to reclaim heat in the waste heat boiler system by-product.Coal gas after waste heat boiler reclaims heat, temperature is down to 316 ℃, enters the particle control device again and removes thin ash in the synthesis gas, and the synthesis gas dust content after the dedusting is less than 0.1ppm (wt).
Coal gas after filtering enters the washing of Venturi scrubber, scrubbing tower and is cooled to fed downstream clean unit behind 150 ℃ and the saturated vapor.
150 ℃ the raw gas that is come by the upstream coal gasification apparatus enters the COS hydrolysis reactor be heated to 170～220 ℃ by middle pressure steam in the raw gas steam heater after, and coal gas enters from the hydrolysis reactor top, and following reaction takes place in reactor:
COS+H
2O＝＝H
2S+CO
2
Go out the raw gas of COS hydrolysis reactor and carry out heat exchange from methyl diethanolamine (MDEA) deacidifying device purified gas, purified gas is heated, and raw gas is cooled.After being heated to 165 ℃, purified gas is sent to the fuel engine power generation system.
Contain 17.0%H in the above-mentioned synthesis gas
2O (volume), and 0.478%NH is arranged
3(volume).By under the equal gas source condition in laboratory, estimating, at volume content 17.0%H
2Under the O condition, Huashuo Science Co., Ltd's research and development are at present produced and two kinds of alumina series catalyst (patent CN01106660.1 and 201110250178.8) of obtaining large-scale application all can cause 1.5% above CO gas generation CO+H
2O==H
2+ CO
2The conversion side reaction has consumed mass efficient composition CO, causes the synthesis gas calorific value to descend, and Titanium series catalyst both domestic and external (as the CRS-31 of AXENS company catalyst) is not though CO+H takes place
2O==H
2+ CO
2Tangible claus reaction has taken place but observe in the experiment in the conversion side reaction under the micro amount of oxygen condition, produce sulphur, and the sulphur oxidation generates SO
2And SO
3, again with a large amount of NH in the synthesis gas
3Reaction generates ammonium sulfate, and the blocking catalyst endoporus causes catalysqt deactivation.
Summary of the invention:
The objective of the invention is can't satisfy at high water content at existing catalyst, COS hydrolysis requirement in the high ammonia content synthesis gas provides a kind of method for hydrolysis based on the ciculation fluidized gasifying process synthesis gas components of high density COS, and this method can be with volume content 17.0%H
2O, 0.478%NH
3Synthesis gas in the COS of 80～120ppm be converted into H
2S, outlet COS content is less than 10ppm, and CO+H takes place in the CO less than 0.5% in the synthesis gas simultaneously
2O==H
2+ CO
2The conversion side reaction, 0.478%NH
3To the active not influence of DJ-1A multifunctional purifying agent.
The objective of the invention is to realize by following method:
A kind of method for hydrolysis based on COS in the ciculation fluidized gasifying process synthesis gas of high density, its gasification mode is air gasification, and the gasification operation temperature is 920～1150 ℃, and vapor pressure scope 2.7～3.3MPa is 2.5～4.5 according to different coal oxygen coals than scope; Its typical synthesis gas volume consists of: 41.587%N
2, 0.1～1%O
2, 7.5%CO
2, 19.791%CO, 12.5%H
2, 17.0%H
2O, 0.478%NH
3, 0.083%H
2S, 80～120ppmCOS, 20ppmHCN is characterized in that: synthesis gas is enterprising to go out reactor through the agent of interior dress DJ-1A multifunctional purifying on going out down or advancing down, and the COS of 80～120ppm in the synthesis gas is converted into H
2S exports COS content less than 10ppm, 170～220 ℃ of reactor operating temperatures, pressure 2.7～3.3MPa, air speed 1000～3000h
-1
Of the present invention based in the COS method for hydrolysis in the ciculation fluidized gasifying process synthesis gas of high density, used DJ-1A multifunctional purifying agent has following feature:
(1) the chemical composition percentage by weight is: Mo
2O
30.1～5%, CuO 0.1～5%, Na
2O 3～9%, and MgO 0.1～10%, and CoO 0.5～2%, Cr
2O
30.1～5%, Al
2O
378～85%, each component sum equals 100%;
(2) granularity: the spheric granules of diameter 2～6mm;
(3) intensity: 〉=20 newton/;
(4) specific area: 100～350 meters squared per gram;
(5) bulk density: 0.6～1.0 kilogram/liter.
Of the present invention based in the COS method for hydrolysis in the ciculation fluidized gasifying process synthesis gas of high density, used DJ-1A multifunctional purifying agent can will contain volume 17.0%H
2O, 0.478%NH
3Synthesis gas in the COS of 80～120ppm be converted into H
2S, outlet COS content is less than 10ppm, and CO+H takes place in the CO gas less than 0.5% volume in the synthesis gas simultaneously
2O==H
2+ CO
2The conversion side reaction, contain volume 0.478%NH
3To the active not influence of DJ-1A multifunctional purifying agent.
The present invention compares with existing COS technology for hydrolyzing, has following characteristics:
(1) be 17.0%H at volume content
2O, 0.478%NH
3Synthesis gas in, can be that the COS of 80～120ppm is converted into H with volume content
2S, outlet COS volume content is less than 10ppm;
(2) CO+H under the high water content
2O==H
2+ CO
2The conversion side reaction is little, and CO+H takes place the CO less than 0.5% volume in the synthesis gas
2O==H
2+ CO
2The conversion side reaction, being significantly less than present COS technology for hydrolyzing has the CO of 1.5～3.0% volumes that this side reaction takes place;
(3) the DJ-1A multifunctional purifying agent used of this COS method for hydrolysis is carrier with aluminium oxide, compares with the CRS-31 catalyst that with titanium dioxide is the AXENS company of carrier, and claus reaction does not take place, and contains the NH of 0.478% volume in the synthesis gas
3Can not cause catalysqt deactivation.
The specific embodiment
Further specify the present invention with example below:
Below among 1～5 embodiment synthesis gas volume form and be: 41.587%N
2, 0.1～1%O
2, 7.5%CO
2, 19.791%CO, 12.5%H
2, 17.0%H
2O, 0.478%NH
3, 0.083%H
2S, 20ppmHCN has only COS content difference.
Embodiment 1:
COS content 80ppm in the synthesis gas, 170 ℃ of serviceability temperatures, pressure 2.7MPa, air speed 1000h
-1, through COS content 6ppm after the agent of DJ-1A multifunctional purifying, CO+H takes place in 0.05% CO
2O==H
2+ CO
2The conversion side reaction.
Embodiment 2:
COS content 90ppm in the synthesis gas, 180 ℃ of serviceability temperatures, pressure 2.8MPa, air speed 1500h
-1, through COS content 7ppm after the agent of DJ-1A multifunctional purifying, CO+H takes place in 0.1% CO
2O==H
2+ CO
2The conversion side reaction.
Embodiment 3:
COS content 100ppm in the synthesis gas, 190 ℃ of serviceability temperatures, pressure 2.9MPa, air speed 2000h
-1, through COS content 8ppm after the agent of DJ-1A multifunctional purifying, CO+H takes place in 0.2% CO
2O==H
2+ CO
2The conversion side reaction.
Embodiment 4:
COS content 110ppm in the synthesis gas, 210 ℃ of serviceability temperatures, pressure 3.1MPa, air speed 2500h
-1, through COS content 7.5ppm after the agent of DJ-1A multifunctional purifying, CO+H takes place in 0.3% CO
2O==H
2+ CO
2The conversion side reaction.
Embodiment 5:
COS content 120ppm in the synthesis gas, 220 ℃ of serviceability temperatures, pressure 3.3MPa, air speed 3000h
-1, through COS content 8.5ppm after the agent of DJ-1A multifunctional purifying, CO+H takes place in 0.4% CO
2O==H
2+ CO
2The conversion side reaction.
Claims (2)
1. one kind based on COS method for hydrolysis in the ciculation fluidized gasifying process synthesis gas of high density, and its gasification mode is air gasification, and the gasification operation temperature is 920～1150 ℃, and vapor pressure scope 2.7～3.3MPa is 2.5～4.5 according to different coal oxygen coals than scope; Its typical synthesis gas volume consists of: 41.587%N
2, 0.1 ~ 1%O
2, 7.5 %CO
2, 19.791%CO, 12.5%H
2, 17.0%H
2O, 0.478%NH
3, 0.083%H
2S, 80 ~ 120ppmCOS, 20ppmHCN is characterized in that: synthesis gas is enterprising to go out reactor through the agent of interior dress DJ-1A multifunctional purifying on going out down or advancing down, and the COS of 80 ~ 120ppm in the synthesis gas is converted into H
2S exports COS content less than 10ppm, 170 ~ 220 ℃ of reactor operating temperatures, pressure 2.7 ~ 3.3MPa, air speed 1000 ~ 3000h
-1Used DJ-1A multifunctional purifying agent has following feature:
(1) the chemical composition percentage by weight is: Mo
2O
30.1 ~ 5%, CuO 0.1 ~ 5%, Na
2O 3 ~ 9%, and MgO 0.1 ~ 10%, and CoO 0.5 ~ 2%, Cr
2O
30.1 ~ 5%, Al
2O
378 ~ 85%, each component sum equals 100%;
(2) granularity: the spheric granules of diameter 2 ~ 6mm;
(3) intensity: 〉=20 newton/;
(4) specific area: 100 ~ 350 meters squared per gram;
(5) bulk density: 0.6 ~ 1.0 kilogram/liter.
2. according to claim 1ly it is characterized in that based on COS method for hydrolysis in the ciculation fluidized gasifying process synthesis gas of high density the agent of described DJ-1A multifunctional purifying can be 17.0%H with volume content
2O, 0.478%NH
3Synthesis gas in the COS of 80 ~ 120ppm be converted into H
2S, outlet COS volume content is less than 10ppm, and CO+H takes place in the CO gas less than 0.5% volume in the synthesis gas simultaneously
2O==H
2+ CO
2The conversion side reaction, contain volume 0.478%NH
3To the active not influence of DJ-1A multifunctional purifying agent.
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|---|---|---|---|
| CN 201110306401 CN102408923B (en) | 2011-10-11 | 2011-10-11 | Hydrolysis method of COS in synthesis gas based on high-density circulating fluidization and gasification process |
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| CN102408923B true CN102408923B (en) | 2013-07-17 |
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Families Citing this family (1)
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| CN103361127A (en) * | 2013-06-25 | 2013-10-23 | 华烁科技股份有限公司 | Purification method for COS (carbonyl sulfide) and HCN (hydrogen cyanide) in integrated gasification combined cycle power generation gas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1135456A (en) * | 1996-01-11 | 1996-11-13 | 湖北省化学研究所 | Active-carbon finely sweetening agent and preparation thereof |
| CN1189394A (en) * | 1997-12-26 | 1998-08-05 | 太原理工大学 | Normal atmospheric temp. and low temp. organic sulphur hydrolyst and its prepn. |
| CN1844326A (en) * | 2006-03-30 | 2006-10-11 | 湖北省化学研究院 | Process for preparing high purity carbon monoxide gas by desulfurization of organic sulfur at low and normal temperature |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7655213B2 (en) * | 2008-05-13 | 2010-02-02 | General Electric Company | Direct oxidation of sulfur with carbon dioxide recycle |
| US20100327224A1 (en) * | 2009-06-26 | 2010-12-30 | Manuela Serban | Compounds for Desulfurization of Hot Fuel Gases |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1135456A (en) * | 1996-01-11 | 1996-11-13 | 湖北省化学研究所 | Active-carbon finely sweetening agent and preparation thereof |
| CN1189394A (en) * | 1997-12-26 | 1998-08-05 | 太原理工大学 | Normal atmospheric temp. and low temp. organic sulphur hydrolyst and its prepn. |
| CN1844326A (en) * | 2006-03-30 | 2006-10-11 | 湖北省化学研究院 | Process for preparing high purity carbon monoxide gas by desulfurization of organic sulfur at low and normal temperature |
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