CN101703883B - Method for depriving sulfureted hydrogen in biogas and device - Google Patents
Method for depriving sulfureted hydrogen in biogas and device Download PDFInfo
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- CN101703883B CN101703883B CN2009102124402A CN200910212440A CN101703883B CN 101703883 B CN101703883 B CN 101703883B CN 2009102124402 A CN2009102124402 A CN 2009102124402A CN 200910212440 A CN200910212440 A CN 200910212440A CN 101703883 B CN101703883 B CN 101703883B
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- biogas
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- column plate
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- oxidation device
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Abstract
The invention provides a method for depriving sulfureted hydrogen in biogas, which is characterized by comprising the following steps: firstly, introducing the biogas into a bubble column plate absorption oxidation device, and absorbing sulfureted hydrogen in the biogas by utilizing sprayed absorption solution containing an oxidant; secondly, controlling the air velocity in a hollow tower of the bubble column plate absorption oxidation device to be 0.2-1.5m/s, wherein the height of the liquid on a plate grid is 0.2-0.8m; and finally sending the biogas absorbed by absorption solution to a subsequent dry-type desulfurizing tower, a wet-type desulfurizing tower or a biological desulfurizing tower for depriving sulfureted hydrogen further. The invention also discloses three devices for depriving sulfureted hydrogen in the biogas by utilizing the combination of the bubble column plate absorption oxidation devices, a desulfuration device using the common dry method and wet method. The invention has simple method, and can effectively and quickly carry out desulfuration at constant pressure.
Description
Technical field
The present invention relates to a kind of green technology, especially requisite desulfur technology and device in the regeneration of biogas, specifically a kind of method and device that removes hydrogen sulfide in the biogas.
Background technology
In biogas such as biogas, digestion gas, rubbish landfill gas, all contain hydrogen sulfide gas, its concentration range ppm from up to a hundred to up to ten thousand.In the above-mentioned biogas process of industrialized utilization, need hydrogen sulfide is wherein removed.
Desulfur technology commonly used at present has dry method, wet method and biological desulphurization.Dry desulfurization mainly is the adsorbent that adopts based on iron oxide or active carbon, and wet desulphurization is mainly the wet oxidation catalysis method, and biological desulphurization then adopts thiophilic to carry out desulfurization by dripping the filter bed reactor.Existence needs improved problem to above-mentioned technology using all: for dry desulfurization, because online regeneration is very loaded down with trivial details, and superheating phenomenon appears easily, and be that the desulfurizing agent after saturated is changed processing in actual applications substantially, cause situations such as operating cost is higher, operation inconvenience like this.And the wet desulphurization technology is mainly derived from the sour gas desulfur technology in the chemical industry, because desulfurizing tower is to work under pressurized conditions in original technology, then is normal pressure in the biogas desulfurization, or even little negative pressure, cause the mass transfer power in the desulfurizing tower to weaken, reduced desulfurized effect.And the processing load owing to Biotrickling filter is limited in the biological desulphurization tower, makes that the bio-trickling bed volume is bigger than normal, causes the desulfurizing tower cost to increase.
Summary of the invention
The objective of the invention is can not directly apply in the very little biogas desulfurization of pressure at existing dry type and wet type desulfurizing technology and cause the biogas desulfuration efficiency low, the problem that operating cost is high is invented a kind of method and device that removes hydrogen sulfide in the biogas.
One of technical scheme of the present invention is:
A kind of method that removes hydrogen sulfide in the biogas is characterized in that it may further comprise the steps:
At first, biogas is entered in the bubbling column plate absorption oxidation device, utilize the absorption liquid that contains oxidant of spray that the hydrogen sulfide in the biogas is absorbed, described absorption liquid is Na
2CO
3/ NaHCO
3Or Na
2CO
3/ NaHCO
3With the compositional liquor of high price molysite complex compound, composite ratio is 1: 0.5～5, and described oxidant is one or more compound in ozone, hydrogen peroxide or the potassium permanganate, and wherein the concentration range of ozone is: 0.2-10g/m
3, the concentration range of hydrogen peroxide is: 50-1000mg/L, the concentration range of potassium permanganate: 20-200mg/L; The consumption of oxidant accounts for the 0.2-1.0% that whole liquid is received liquid;
Secondly, the void tower air velocity is 0.2-1.5m/s in the control bubbling column plate absorption oxidation device, the high 0.2-0.8m of liquid on the screen;
At last, will send into the further hydrogen sulfide of removing in follow-up dry type desulfurizing tower, wet type desulfurizing tower or the biological desulphurization tower through the biogas that absorption liquid absorbs.
Described bubbling column plate absorption oxidation device is mainly by housing 1, the bottom of housing 1 is provided with biogas air inlet 2, the top of housing 1 is provided with the biogas outlet, in housing 1, advance mouthfuls 2 above screen 3 is installed, screen 3 is provided with a plurality of bubble-caps 4, and the top of bubble-cap 4 is equipped with shower 5, and shower 5 links to each other with the absorption liquid conveying device that is added with oxidant, be coated with downspout 6 on screen 3, the upper end of downspout 6 exceeds the upper surface 0.2-0.8m of screen 3.
Two of technical scheme of the present invention is:
A kind of device that removes hydrogen sulfide in the biogas, it is characterized in that it mainly is made up of bubbling column plate absorption oxidation device 7 and dry type desulfurizing tower 8, and dry type desulfurizing tower 8 is positioned at the top of bubbling column plate absorption oxidation device 7, separate by top grating 9 between the two, top grating 9 is provided with gas outlet 10 as the air inlet of dry type desulfurizing tower 8 on the top of dry type desulfurizing tower 8; Described bubbling column plate absorption oxidation device 7 is mainly by housing 1, the bottom of housing 1 is provided with biogas air inlet 2, the top of housing 1 is provided with the biogas outlet, in housing 1, advance mouthfuls 2 above screen 3 is installed, screen 3 is provided with a plurality of bubble-caps 4, and the top of bubble-cap 4 is equipped with shower 5, and shower 5 links to each other with the absorption liquid conveying device that is added with oxidant, be coated with downspout 6 on screen 3, the upper end of downspout 6 exceeds the upper surface 0.2-0.8m of screen 3.
Three of technical scheme of the present invention is:
A kind of device that removes hydrogen sulfide in the biogas, it is characterized in that it mainly is made up of bubbling column plate absorption oxidation device 7 and wet type desulfurizing tower 11, and wet type desulfurizing tower 11 is positioned at the top of bubbling column plate absorption oxidation device 7, separate by dividing plate 12 between the two, air-lift tube 13 and downspout 14 are installed on the dividing plate 12, the lower end of downspout 14 is stretched out with regeneration of absorption solution EGR 15 from the bottom of bubbling column plate absorption oxidation device 7 and is linked to each other, and is provided with gas outlet 10 on the top of wet type desulfurizing tower 11; Described bubbling column plate absorption oxidation device 7 is mainly by housing 1, the bottom of housing 1 is provided with biogas air inlet 2, the top of housing 1 is provided with the biogas outlet, in housing 1, advance mouthfuls 2 above screen 3 is installed, screen 3 is provided with a plurality of bubble-caps 4, and the top of bubble-cap 4 is equipped with shower 5, and shower 5 links to each other with the absorption liquid conveying device that is added with oxidant, be coated with downspout 6 on screen 3, the upper end of downspout 6 exceeds the upper surface 0.2-0.8m of screen 3.
Beneficial effect of the present invention:
The inventive method is simple, and desulfuration efficiency is good, and the efficient height is particularly useful for the desulfurization of normal pressure and little negative pressure biogas.The content of hydrogen sulfide is well below the setting of national standard in the biogas after method and apparatus of the present invention is handled.
(1) the present invention adopts the prime unit of bubbling column plate absorption oxidation device as desulfurization, and hybrid oxidant is strengthened oxidation in absorption liquid.
(2) oxidant of the present invention is that in ozone or hydrogen peroxide or the potassium permanganate one or more are compound, and concentration range is ozone: 0.2-10g/m3, and the hydrogen peroxide concentration scope is: 50-1000mg/L, potassium permanganate concentration range: 20-200mg/L.Absorption liquid adopts conventional Na
2CO
3/ NaHCO
3Or Na
2CO
3/ NaHCO
3Compositional liquor with high price molysite complex compound.Renewable circulation of absorption liquid after the work or directly discharging.
(3) bubbling column plate hollow tower air velocity of the present invention is 0.2-1.5m/s, the high 0.2-0.8m of liquid on the screen.
(4) bubbling column plate absorption oxidation device of the present invention and dry type desulfurizing tower or wet type desulfurizing tower or biological desulphurization tower can be integrated in the cell arrangement, and also the front and back level is provided with independently.
Description of drawings
Fig. 1 is the structural representation of bubbling column plate absorption oxidation device of the present invention.
Fig. 2 is one of structural representation of desulfurizer of the present invention.
Fig. 3 be desulfurizer of the present invention structural representation two.
The specific embodiment
The present invention is further illustrated below in conjunction with drawings and Examples.
Embodiment one.
As shown in Figure 1.
A kind of method that removes hydrogen sulfide in the biogas, it may further comprise the steps:
At first, biogas is entered in the bubbling column plate absorption oxidation device, utilize the absorption liquid that contains oxidant of spray that the hydrogen sulfide in the biogas is absorbed, described absorption liquid is Na
2CO
3/ NaHCO
3Or Na
2CO
3/ NaHCO
3With the compositional liquor of high price molysite complex compound, composite ratio is 1: 0.5～5 mass percent, wherein Na
2CO
3/ NaHCO
3Or Na
2CO
3/ NaHCO
3Mass ratio be 1, the mass ratio of high price molysite complex compound is 0.5～5, high price iron (referring to ferric iron) salt complex can be EDTA complexing iron, sulfosalicylic acid complexing iron, triethanolamine complexing iron etc.: described oxidant is one or more compound in ozone, hydrogen peroxide or the potassium permanganate, and wherein the concentration range of ozone is: 0.2～10g/m
3, the concentration range of hydrogen peroxide is: 50～1000mg/L, the concentration range of potassium permanganate: 20～200mg/L; The consumption of oxidant account for whole liquid receive liquid long-pending 0.2～1.0%; During concrete enforcement, those skilled in the art or carry out the assembly of arbitrary proportion according to the ratio of present embodiment.
Secondly, the void tower air velocity is 0.2-1.5m/s in the control bubbling column plate absorption oxidation device, the high 0.2-0.8m of liquid on the screen;
At last, will send into the further hydrogen sulfide of removing in follow-up dry type desulfurizing tower, wet type desulfurizing tower or the biological desulphurization tower through the biogas that absorption liquid absorbs.
Bubbling column plate absorption oxidation device wherein as shown in Figure 1, it is mainly by housing 1, the bottom of housing 1 is provided with biogas air inlet 2, the top of housing 1 is provided with biogas outlet, in housing 1, advance institute's mouth 2 above screen 3 is installed, screen 3 is provided with a plurality of bubble-caps 4, the top of bubble-cap 4 is equipped with shower 5, shower 5 links to each other with the absorption liquid conveying device that is added with oxidant, is coated with downspout 6 on screen 3, and the upper end of downspout 6 exceeds the upper surface 0.2-0.8m of screen 3.
Embodiment two.
As shown in Figure 2.
A kind of device that removes hydrogen sulfide in the biogas, it mainly is made up of bubbling column plate absorption oxidation device 7 and dry type desulfurizing tower 8, and dry type desulfurizing tower 8 is positioned at the top of bubbling column plate absorption oxidation device 7, separate by top grating 9 between the two, top grating 9 is as the air inlet of dry type desulfurizing tower 8, be provided with gas outlet 10 on the top of dry type desulfurizing tower 8, the bottom of gas outlet 10 is provided with charge door 16, charge door 16 bottoms are desulfurizing agent layers 18 of the main desulfurization unit of dry type desulfurizing tower, the bottom of desulfurizing agent layer 18 is provided with discharge port, desulfurizing agent layer 18 also is supported in the dry type desulfurizing tower by screen 9, and install the bottom of screen 9 is absorption liquid shower 5 in the bubbling column plate absorption oxidation device 7; Described bubbling column plate absorption oxidation device 7 is mainly by housing 1, the bottom of housing 1 is provided with biogas air inlet 2, the top of housing 1 is provided with the biogas outlet, in housing 1, advance mouthfuls 2 above screen 3 is installed, screen 3 is provided with a plurality of bubble-caps 4, and the top of bubble-cap 4 is equipped with shower 5, and shower 5 links to each other with the absorption liquid conveying device that is added with oxidant, be coated with downspout 6 on screen 3, the upper end of downspout 6 exceeds the upper surface 0.2-0.8m of screen 3.As shown in Figure 2.
Embodiment three.
As shown in Figure 3.
A kind of device that removes hydrogen sulfide in the biogas, it mainly is made up of bubbling column plate absorption oxidation device 7 and wet type desulfurizing tower 11, and wet type desulfurizing tower 11 is positioned at the top of bubbling column plate absorption oxidation device 7, separate by dividing plate 12 between the two, air-lift tube 13 and downspout 14 are installed on the dividing plate 12, the lower end of downspout 14 is stretched out with regeneration of absorption solution EGR 15 from the bottom of bubbling column plate absorption oxidation device 7 and is linked to each other, be provided with gas outlet 10 and absorption liquid shower 19 on the top of wet type desulfurizing tower 11, the centre of wet type desulfurizing tower 11 is a packing layer 21, packing layer 21 is bearing on the top grating 23, the top of packing layer 21 is provided with charge door 20, the bottom is provided with discharge port, and the bottom of screen 23 is dividing plate 12; Described bubbling column plate absorption oxidation device 7 is mainly by housing 1, the bottom of housing 1 is provided with biogas air inlet 2, the top of housing 1 is provided with the biogas outlet, in housing 1, advance mouthfuls 2 above screen 3 is installed, screen 3 is provided with a plurality of bubble-caps 4, and the top of bubble-cap 4 is equipped with shower 5, and shower 5 links to each other with the absorption liquid conveying device that is added with oxidant, be coated with downspout 6 on screen 3, the upper end of downspout 6 exceeds the upper surface 0.2-0.8m of screen 3.As shown in Figure 3.
Again through embodiment two or after implementing three combined apparatus and handling, the biogas of hydrogen sulfide original concentration 8000ppm can be reduced to 10-20ppm through the invention process one preliminary treatment, clearance reaches more than 99%.
Can make hydrogen sulfide content in the biogas be reduced to the setting value of gas equipment, sometimes even be lower than the setting of equipment, have crucial meaning equipment life, can prevent equipment incrustation improving.
The part that the present invention does not relate to prior art that maybe can adopt all same as the prior art is realized.
Claims (3)
1. method that removes hydrogen sulfide in the biogas is characterized in that it may further comprise the steps:
At first, biogas is entered in the bubbling column plate absorption oxidation device, utilize the absorption liquid that contains oxidant of spray that the hydrogen sulfide in the biogas is absorbed, described absorption liquid is Na
2CO
3/ NaHCO
3Or Na
2CO
3/ NaHCO
3With the compositional liquor of high price molysite complex compound, composite ratio is 1: 0.5～5, and described oxidant is one or more compound in ozone, hydrogen peroxide or the potassium permanganate, and wherein the concentration range of ozone is: 0.2-10g/m
3, the concentration range of hydrogen peroxide is: 50-1000mg/L, the concentration range of potassium permanganate: 20-200mg/L; The consumption of oxidant accounts for the 0.2-1.0% of whole absorption liquid;
Secondly, the void tower air velocity is 0.2-1.5m/s in the control bubbling column plate absorption oxidation device, the high 0.2-0.8m of liquid on the screen;
At last, will send into the further hydrogen sulfide of removing in follow-up dry type desulfurizing tower, wet type desulfurizing tower or the biological desulphurization tower through the biogas that absorption liquid absorbs; Described bubbling column plate absorption oxidation device is mainly by housing (1), the bottom of housing (1) is provided with biogas air inlet (2), the top of housing (1) is provided with the biogas outlet, in housing (1), the top of air inlet (2) is equipped with screen (3), screen (3) is provided with a plurality of bubble-caps (4), the top of bubble-cap (4) is equipped with shower (5), shower (5) links to each other with the absorption liquid conveying device that is added with oxidant, be coated with downspout (6) on screen (3), the upper end of downspout (6) exceeds the upper surface 0.2-0.8m of screen (3).
2. device that removes hydrogen sulfide in the biogas, it is characterized in that it mainly is made up of bubbling column plate absorption oxidation device (7) and dry type desulfurizing tower (8), and dry type desulfurizing tower (8) is positioned at the top of bubbling column plate absorption oxidation device (7), separate by top grating (9) between the two, top grating (9) is provided with gas outlet (10) as the air inlet of dry type desulfurizing tower (8) on the top of dry type desulfurizing tower (8); Described bubbling column plate absorption oxidation device (7) is mainly by housing (1), the bottom of housing (1) is provided with biogas air inlet (2), the top of housing (1) is provided with the biogas outlet, in housing (1), the top of air inlet (2) is equipped with screen (3), screen (3) is provided with a plurality of bubble-caps (4), the top of bubble-cap (4) is equipped with shower (5), shower (5) links to each other with the absorption liquid conveying device that is added with oxidant, be coated with downspout (6) on screen (3), the upper end of downspout (6) exceeds the upper surface 0.2-0.8m of screen (3); Described oxidant is that in ozone or hydrogen peroxide or the potassium permanganate one or more are compound, and concentration range is ozone: 0.2-10g/m
3, the hydrogen peroxide concentration scope is: 50-1000mg/L, potassium permanganate concentration range: 20-200mg/L; Described absorption liquid is Na
2CO
3/ NaHCO
3Or Na
2CO
3/ NaHCO
3Compositional liquor with high price molysite complex compound; The void tower air velocity is 0.2-1.5m/s in the bubbling column plate absorption oxidation device, the high 0.2-0.8m of liquid on the screen.
3. device that removes hydrogen sulfide in the biogas, it is characterized in that it mainly is made up of bubbling column plate absorption oxidation device (7) and wet type desulfurizing tower (11), and wet type desulfurizing tower (11) is positioned at the top of bubbling column plate absorption oxidation device (7), separate by dividing plate (12) between the two, air-lift tube (13) and downspout (14) are installed on the dividing plate (12), the lower end of downspout (14) is stretched out with regeneration of absorption solution EGR (15) from the bottom of bubbling column plate absorption oxidation device (7) and is linked to each other, and is provided with gas outlet (10) on the top of wet type desulfurizing tower (11); Described bubbling column plate absorption oxidation device (7) is mainly by housing (1), the bottom of housing (1) is provided with biogas air inlet (2), the top of housing (1) is provided with the biogas outlet, in housing (1), the top of air inlet (2) is equipped with screen (3), screen (3) is provided with a plurality of bubble-caps (4), the top of bubble-cap (4) is equipped with shower (5), shower (5) links to each other with the absorption liquid conveying device that is added with oxidant, be coated with downspout (6) on screen (3), the upper end of downspout (6) exceeds the upper surface 0.2-0.8m of screen (3); Described oxidant is that in ozone or hydrogen peroxide or the potassium permanganate one or more are compound, and concentration range is ozone: 0.2-10g/m
3, the hydrogen peroxide concentration scope is: 50-1000mg/L, potassium permanganate concentration range: 20-200mg/L; Described absorption liquid is Na
2CO
3/ NaHCO
3Or Na
2CO
3/ NaHCO
3Compositional liquor with high price molysite complex compound; The void tower air velocity is 0.2-1.5m/s in the bubbling column plate absorption oxidation device, the high 0.2-0.8m of liquid on the screen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102124402A CN101703883B (en) | 2009-11-11 | 2009-11-11 | Method for depriving sulfureted hydrogen in biogas and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102124402A CN101703883B (en) | 2009-11-11 | 2009-11-11 | Method for depriving sulfureted hydrogen in biogas and device |
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| Publication Number | Publication Date |
|---|---|
| CN101703883A CN101703883A (en) | 2010-05-12 |
| CN101703883B true CN101703883B (en) | 2011-11-09 |
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| CN2009102124402A Expired - Fee Related CN101703883B (en) | 2009-11-11 | 2009-11-11 | Method for depriving sulfureted hydrogen in biogas and device |
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| CN102559313B (en) * | 2011-11-09 | 2016-07-06 | 中国石油大学(华东) | Offshore oil platform natural gas seawater Claus hydrogen sulfide removing process method |
| CN103214124B (en) * | 2013-05-13 | 2014-06-18 | 达州军华油田工程服务有限公司 | Gas production wastewater desulfurization purification pretreatment technology |
| CN104275086B (en) * | 2014-10-28 | 2016-09-28 | 南京大学 | A kind of wet oxidation-desulfurizing method and device |
| CN105879590B (en) * | 2016-06-03 | 2019-02-01 | 北京国电龙源环保工程有限公司 | A kind of spiral-flow type is bubbled coupling high-efficiency desulfurization spray unit and desulfurizing tower |
| CN106823693B (en) * | 2017-03-28 | 2019-08-27 | 中北大学 | A kind of deep desulfuration absorbent for smoke-gas wet desulfurization |
| CN106925097A (en) * | 2017-04-28 | 2017-07-07 | 陶汉中 | It is a kind of based on liquid phase oxidation to the combined column and its technique of flue gas desulfurization and denitrification |
| CN107161956B (en) * | 2017-06-19 | 2020-10-02 | 中国石油大学(华东) | Circular economic process for preparing sulfur by oxidizing hydrogen sulfide by wet method |
| CN109663485B (en) * | 2017-10-17 | 2021-11-05 | 中国石油化工股份有限公司 | Emergency scavenging liquid for hydrogen sulfide gas leakage and application |
| CN108889100A (en) * | 2018-07-04 | 2018-11-27 | 华东理工大学 | A kind of method of oxidation removal hydrogen sulfide |
| CN108751245B (en) * | 2018-09-07 | 2023-09-26 | 南京金焰锶业有限公司 | System and process for removing hydrogen sulfide in strontium sulfide solution carbonization process |
| CN109453637A (en) * | 2018-12-03 | 2019-03-12 | 湖州浙宝钙业科技股份有限公司 | Spray desulfurizer |
| CN111013177B (en) * | 2019-12-16 | 2020-10-20 | 常州大学 | Composite tower plate structure and composite tower equipment |
| CN111330365A (en) * | 2020-03-17 | 2020-06-26 | 孙婷婷 | Collect desulfurization dust removal deodorization in exhaust treatment device of an organic whole |
| CN114686282B (en) * | 2022-04-01 | 2023-04-07 | 中石化江苏石油工程设计有限公司 | Natural gas wet desulphurization device and method |
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