CN102115685B - Method for finely removing hydrogen sulfide from natural gas at normal temperature - Google Patents
Method for finely removing hydrogen sulfide from natural gas at normal temperature Download PDFInfo
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- CN102115685B CN102115685B CN 201110001491 CN201110001491A CN102115685B CN 102115685 B CN102115685 B CN 102115685B CN 201110001491 CN201110001491 CN 201110001491 CN 201110001491 A CN201110001491 A CN 201110001491A CN 102115685 B CN102115685 B CN 102115685B
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- natural gas
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- temperature
- thionizer
- desulfurizing agent
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Abstract
The invention discloses a method for finely removing hydrogen sulfide from natural gas at a normal temperature. The method adopts the following technical scheme: the natural gas enters a fine desulfurizing tower loaded with activated-carbon fine desulfurizing agent after the processes of drying and gas-water separation, so that H2S in the gas is removed under the effect of the desulfurizing agent; the fine desulfurizing agent is filled in a two-layer or multi-layer manner; the total height-to-diameter ratio of a bed layer is 1.5 to 4.0, the temperature is between normal temperature and 150 DEG C, and the pressure is between normal pressure and 2.5MPa; and through the measurement of a sulfur meter, when the contents of H2S in the natural gas reach 5mg/Nm3 after desulfurization through the desulfurizing tower, the desulfurizing process is completed. The desulfurizing agent uses particles or formed activated carbon as carriers of an activated component (i.e. CuO), and the contents of CuOin the desulfurizing agent are 2Wt% to 9Wt%; and the radial crushing strength is larger than or equal to 60N/cm, the bulk density is 0.5kg/I to 0.7kg/I, the specific surface is larger than 140m2/g, and the specific pore volume is 0.4ml/g to 0.8ml/g. Copper-loaded activated carbon is adopted as the desulfurizing agent for desulfurization, so that the special surface structure of the activated-carbon material is utilized for H2S purification through adsorption and catalytic oxidation.
Description
Technical field
The invention belongs to the natural gas conditioning treatment technology, be specifically related to a kind of Sweet natural gas normal temperature sulfur method.
Background technology
Sweet natural gas is as a kind of clean energy, and its development and utilization more and more is subject to people's attention, and there is corresponding purification standard various countries to quality of natural gas.The development gas industry, necessary researchdevelopment gas purifying process solves transporting of Sweet natural gas and lays in and the harmless problem of utilizing.Dry desulfurization is generally adopted in desulfurization, and dry method comprises iron oxide process, zinc oxide method, activated carbon method, sieve method etc., and dry method is applicable to low sulfurous gas processing, is widely used so that its technology is simple, easy to operate, desulfurization precision is high, energy consumption is low.Ferric oxide is because of by the desulfurization of chemical absorption mechanism, thus under aerobic or oxygen-free atmosphere, all can use, but air speed can not be too high, and water tolerance is lower.There are shortcomings such as energy consumption height, the driving time is long, price is expensive in zinc oxide.
Gac class sweetening agent is usually used in removing H in aerobic, the high humidity atmosphere
2S.The tradition active carbon desulfurization is because absorption and speed of reaction are low, and Sulfur capacity is lower, and difficulty reaches industrially desulfurized requirement.
Summary of the invention
In order to overcome the above-mentioned defective that the prior art field exists, the objective of the invention is to, a kind of method of Sweet natural gas constant temperature fine desulfurizing hydrogen is provided, this method has that desulphurization reaction speed is fast, Sulfur capacity is high, can reduce production costs significantly, enhance productivity.
The method of Sweet natural gas constant temperature fine desulfurizing hydrogen provided by the invention, by the following technical solutions: enter the fine removing tower that the activated carbon desulfurizing agent is housed after natural gas via drying, the gas-water separation, under the sweetening agent effect, remove the H in the gas
2S; Desulfurizing agent is divided equally two-layer or multilayer filling, and the total aspect ratio of bed is 1.5-4.0, and temperature is normal temperature ~ 150 ℃, and pressure is normal pressure ~ 2.5Mpa; Measure H in Sweet natural gas after the thionizer desulfurization with sulfur detector
2S content reaches 5mg/Nm
3The time, finish sweetening process.
Described sweetening agent is to be carrier with particle or pressed active carbon, supported active component C uO, and the content of CuO is 2～9Wt% in the sweetening agent.Crush strength 〉=60N/cm radially, bulk density 0.5-0.7kg/l, specific surface〉140m
2/ g, specific pore volume 0.4-0.8ml/g.
Realize that above-mentioned Sweet natural gas normal temperature essence takes off H
2The cardinal principle of S skill is:
CuO+H
2S
CuS ten H
2O ten Q
40－150℃
2H
2S+O
2 
2S ten 2H
2O ten Q
40－150℃
Q is heat in the formula.
After finishing desulfurization operations, thionizer is regenerated, need switch out by the regenerative sulfur binding tower, the regeneration superheated vapour reduces pressure through reducing valve earlier, feed from top of tower, temperature rises gradually in the tower, and the components such as sulfide of steam condensate and solution sucking-off in sweetening agent are discharged by the thionizer bottom; Steam flow control is at 10 m
3/ minute, along with the carrying out of regeneration, bed temperature rises gradually, rises to 100 ℃～105 ℃, continues 20 minutes, then bed temperature is risen to about 180～200 ℃.Per 20 minutes sampling analysis are analyzed sulfide content index in the resurgent gases, H in resurgent gases
2S content is less than 1 mg/ m
3The time, regeneration is finished.
After regeneration is finished, must carry out drying to thionizer and pipeline; At first through the nitrogen heater heating, adopt low-pressure steam to be heated to 120～150 ℃ from the nitrogen outside the battery limit (BL), after reducing valve is decompressed to 0.2MPaA, feed thionizer from the bottom again; Impurity such as regeneration back residuary water steam, sulfide are taken out of through hot nitrogen purging drying in the tower; Nitrogen flow control is at 30m
3/ minute, by analyzing water-content in the dry waste gas less than 0.5 g/m
3The time, determine that drying finishes, working pressure 0.2MPaA in the tower, service temperature is 142～150 ℃.
The method of Sweet natural gas constant temperature fine desulfurizing hydrogen provided by the invention, its beneficial effect are, adopt Activated Carbon with Cu to carry out desulfurization as sweetening agent, utilize the special surface structure of absorbent charcoal material, realize H by absorption, oxidation
2The purification of S.This process has characteristics such as desulphurization reaction speed is fast, Sulfur capacity height, has increased substantially production efficiency; Sweetening agent can be regenerated, and recycling economizes on resources in a large number, has reduced production cost significantly.
Embodiment
Below in conjunction with an embodiment, the method for Sweet natural gas constant temperature fine desulfurizing hydrogen provided by the invention is described in detail.
Embodiment
The method of the Sweet natural gas constant temperature fine desulfurizing hydrogen of present embodiment is carried out cleaning and desulfurization to the Sweet natural gas in the color southern 2# gas station of Xinjiang Oilfield Company and Shi Xi oil field and is handled, and sulphur content is all above the 20mg/m of national Specification in the Sweet natural gas of this oil field output
3, the main component of this Sweet natural gas: contain CH
487.77%, C
25.28%, C
32.26%, C
41.37%, C
50.5%, C
60.21%, CO2 0.88%, N
21.68%, H
2S 300 ~ 600mg/Nm
3
Enter the fine removing tower that the activated carbon desulfurizing agent is housed after above-mentioned natural gas via drying, the gas-water separation, under the sweetening agent effect, remove the H in the gas
2S; Desulfurizing agent is divided equally two-layer or the multilayer filling, and the total aspect ratio of bed is 3.0, and temperature is normal temperature, and pressure is normal pressure; Measure H in Sweet natural gas after the thionizer desulfurization with sulfur detector
2S content reaches 5mg/Nm
3The time, finish sweetening process.
Described sweetening agent is to be carrier with particle or pressed active carbon, supported active component C uO, and the content of CuO is 7Wt% in the sweetening agent.Crush strength 〉=60N/cm radially, bulk density 0.6 kg/l, specific surface〉140m
2/ g, specific pore volume 0.4-0.8ml/g.
Present embodiment adopts 2 thionizers, and refined active carbon desulfurizer all is housed in the thionizer.Sweet natural gas from Sweet natural gas separating tank outside the battery limit (BL) enters from " first thionizer " top, discharges from the bottom, enters from " second adsorption tower " top again, discharges from the bottom, and namely output high-purity natural gas is sent the battery limit (BL) through the discharging pipeline.
After finishing desulfurization operations, thionizer is regenerated, according to the thief hatch analytical results of taking from two thionizers series connection intermediate line positions, think that " first adsorption tower " bed has penetrated or approach when penetrating, namely switch, then the inactivation sweetening agent is regenerated.
Need switch out by the regenerative sulfur binding tower, the superheated vapour of regenerating feeds from top of tower earlier through the reducing valve decompression, and temperature rises gradually in the tower, and the components such as sulfide of steam condensate and solution sucking-off in sweetening agent are discharged by the thionizer bottom; Steam flow control is at 10 m
3/ minute, along with the carrying out of regeneration, bed temperature rises gradually, rises to 102 ℃, continues 20 minutes, then bed temperature is risen to about 190 ℃.Per 20 minutes sampling analysis are analyzed sulfide content index in the resurgent gases, H in resurgent gases
2S content is less than 1 mg/ m
3The time, regeneration is finished.
After regeneration is finished, must carry out drying to thionizer and pipeline; At first through the nitrogen heater heating, adopt low-pressure steam to be heated to 130 ℃ from the nitrogen outside the battery limit (BL), after reducing valve is decompressed to 0.2MPaA, feed thionizer from the bottom again; Impurity such as regeneration back residuary water steam, sulfide are taken out of through hot nitrogen purging drying in the tower; Nitrogen flow control is at 30 m
3/ minute, by analyzing water-content in the dry waste gas less than 0.5 g/m
3The time, determine that drying finishes, working pressure 0.2MPaA in the tower, service temperature is 145 ℃.
Present embodiment has only provided under the normal temperature and pressure conditions, the technology of the smart depriving hydrogen sulphide of Sweet natural gas, if temperature and pressure is suitably improved, for example temperature is 50 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃, when pressure was condition such as 1.5 Mpa, 1.8 Mpa, 2.0 Mpa, 2.3 Mpa, 2.5 Mpa, sweetening effectiveness can be better.
Claims (2)
1. the method for a Sweet natural gas constant temperature fine desulfurizing hydrogen is characterized in that: enter after natural gas via drying, the gas-water separation and be equipped with
The fine removing tower of refined active carbon desulfurizer under the sweetening agent effect, removes the H in the gas
2S;
Refined active carbon desulfurizer is to be carrier with particle or pressed active carbon, supported active component C uO, and the content of CuO is 2 ~ 9Wt% in the sweetening agent, crush strength 〉=60N/cm radially, bulk density 0.5-0.7kg/l, specific surface＞140m
2/ g, specific pore volume 0.4-0.8ml/g, desulfurizing agent divide equally two-layer or multilayer filling, and the total aspect ratio of bed is 1.5-4.0, and temperature is normal temperature ~ 150 ℃, and pressure is normal pressure ~ 2.5Mpa, measures H in Sweet natural gas after the thionizer desulfurization with sulfur detector
2S content reaches 5mg/Nm
3The time, finish sweetening process;
After finishing desulfurization operations, thionizer is regenerated, need switch out by the regenerative sulfur binding tower, the regeneration superheated vapour reduces pressure through reducing valve earlier, feed from top of tower, temperature rises gradually in the tower, and the components such as sulfide of steam condensate and solution sucking-off in sweetening agent are discharged by the thionizer bottom; Steam flow control is at 10m
3/ minute, along with the carrying out of regeneration, bed temperature rises gradually, rises to 100 ℃ ~ 105 ℃, continues 20 minutes, then bed temperature is risen to about 180 ~ 200 ℃; Per 20 minutes sampling analysis are analyzed sulfide content index in the resurgent gases, H in resurgent gases
2S content is less than 1mg/m
3The time, regeneration is finished.
2. the method for Sweet natural gas constant temperature fine desulfurizing hydrogen according to claim 1 is characterized in that: after regeneration is finished, must carry out drying to thionizer and pipeline; At first through the nitrogen heater heating, adopt low-pressure steam to be heated to 120 ℃ ~ 150 ℃ from the nitrogen outside the battery limit (BL), after reducing valve is decompressed to 0.2MpaA, feed thionizer from the bottom again; The impurity such as the residual water vapor in back, sulfide of regenerating in the tower purge drying through hot nitrogen and take out of; Nitrogen flow control is at 30m
3/ minute, by analyzing water-content in the dry waste gas less than 0.5g/m
3The time, determine that drying finishes, working pressure 0.2MpaA in the tower, service temperature is 142 ~ 150 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110001491 CN102115685B (en) | 2011-01-06 | 2011-01-06 | Method for finely removing hydrogen sulfide from natural gas at normal temperature |
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|---|---|---|---|
| CN 201110001491 CN102115685B (en) | 2011-01-06 | 2011-01-06 | Method for finely removing hydrogen sulfide from natural gas at normal temperature |
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| CN102115685A CN102115685A (en) | 2011-07-06 |
| CN102115685B true CN102115685B (en) | 2013-10-02 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106606926A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Room temperature fine desulfurization method |
| CN106000354A (en) * | 2016-06-13 | 2016-10-12 | 孟红琳 | Preparation method of methyl tertiary butyl ether desulfurization adsorbent |
| CN106008176A (en) * | 2016-06-13 | 2016-10-12 | 孟红琳 | Desulfuration refining method of methyl tertiary butyl ether |
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| CN101524640A (en) * | 2009-04-23 | 2009-09-09 | 中国海洋石油总公司 | On-line regenerating method of oil product desulfurizing and denitrifying absorbent |
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| CN101721833A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | Method for recovering and purifying hydrocarbon wastegas by condensation and adsorption |
| CN101862640A (en) * | 2010-06-28 | 2010-10-20 | 克拉玛依金叶化工有限责任公司 | Method for preparing desulfurizer used for removing H2S from natural gas |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5719016A (en) * | 1980-07-08 | 1982-02-01 | Ishikawajima Harima Heavy Ind Co Ltd | Dry type flue-gas desulfurization apparatus |
-
2011
- 2011-01-06 CN CN 201110001491 patent/CN102115685B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1130151A (en) * | 1995-12-20 | 1996-09-04 | 湖北省化学研究所 | Inversion absorption type constant temperature fine desulfurizing technology |
| CN1324686A (en) * | 2000-05-24 | 2001-12-05 | 湖北省化学研究所 | Refined active carbon desulfurizer for eliminating mercaptan and thioether and its prepn. |
| CN1634651A (en) * | 2003-12-30 | 2005-07-06 | 中国石油化工股份有限公司 | Regeneration method of desulfurization adsorbent |
| CN101126042A (en) * | 2007-09-28 | 2008-02-20 | 四川省达科特化工科技有限公司 | Integrative purification and separation method for natural gas |
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Inventor after: Xi Huimin Inventor after: Fan Hui Inventor after: Sun Wencheng Inventor after: Yang Yuyao Inventor after: Chen Lujian Inventor after: Liu Xiaoqun Inventor after: Zhao Hong Inventor after: Zeng Jian Inventor before: Xi Huimin Inventor before: Sun Wencheng Inventor before: Yang Zili Inventor before: Fan Hui Inventor before: Chen Lujian Inventor before: Zhao Hong Inventor before: Zeng Jian |
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Free format text: CORRECT: INVENTOR; FROM: XI HUIMIN SUN WENCHENG YANG ZILI FAN HUI CHEN LUJIAN ZHAO HONG ZENG JIAN TO: XI HUIMIN FAN HUI SUN WENCHENG YANG YUYAO CHEN LUJIAN LIU XIAOQUN ZHAO HONG ZENG JIAN |
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Granted publication date: 20131002 Termination date: 20210106 |