CN103801183A - Method for removing H2S in offshore oil production associated gas by utilizing seawater modified LO-CATII method - Google Patents
Method for removing H2S in offshore oil production associated gas by utilizing seawater modified LO-CATII method Download PDFInfo
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- CN103801183A CN103801183A CN201210457932.XA CN201210457932A CN103801183A CN 103801183 A CN103801183 A CN 103801183A CN 201210457932 A CN201210457932 A CN 201210457932A CN 103801183 A CN103801183 A CN 103801183A
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Abstract
The invention discloses a method for removing H2S in offshore oil production associated gas by utilizing seawater modified LO-CATII process. The method comprises the steps of leading simulated natural gas containing H2S into redox medium absorption liquid prepared by seawater in which a catalyst and a complexing agent are added, blowing a certain amount of air into the adsorption liquid, replacing part of absorption liquid to continue to desulfurize when the concentration of H2S at a reactor outlet exceeds an index. After the product sulfur in the replaced absorption liquid is filtered, the replaced absorption liquid can be recycled through air regeneration. The method has the advantages that the deficiencies that the conventional desulfurization method has hidden pollution to a sea, the desulfurization liquid is toxic and inflammable, the occupied area is large and the like can be overcome, the technological requirement on the limited volume of an offshore oil production platform and low temperature, low pressure and high-safety coefficients can be met, and the method can comply with the development trend of blue ocean economy.
Description
Technical field
The present invention relates to one and remove H in offshore drilling platform oil recovery associated gas
2the novel method of S, more specifically says a kind of and utilizes the alkalescence of seawater and " pH sustained release agent " effect to remove H in offshore drilling platform associated gas, natural gas field in conjunction with the seawater LO-CAT II method of the LO-CAT II sulfur removal technology formation of modification
2the method of S.
Background technology
Along with the arrival in low-carbon economy epoch, natural gas will exceed crude oil and coal, become " chief energy " in primary energy consumption structure, enter the brand-new development utilization epoch.Within 2000～2008 years, China's natural gas consumption figure is by 2.45 × 10
10m
3be increased to 8.07 × 10
10m
3, and present the trend of rapid growth.But, with respect to land natural gas, the shortcoming such as offshore natural gas exploitation exists environment sternness, technical sophistication, investment is large, the cycle is long.What obtain at present exploitation is mainly the natural gas field in coastal waters, and when offshore oilfield association tolerance is less, general whole emptying is burnt; When associated gas is more, be mainly used in power station and heat station demand for fuel, remain a small amount of emptying.But in associated gas, conventionally contain a small amount of H
2s, CO
2deng impurity, when it is during for power station and heat station fuel, can cause heavy corrosion to generator, equipment pipe etc., the SO that burning is emitted
xgas can pollute atmosphere, causes acid rain and greenhouse effects and damages the ozone layer.Therefore, the H in associated gas
2s need to just can be used after desulfurization is processed.
The industrialized H that removes both at home and abroad at present
2s technique has a lot, is mainly divided into two kinds of dry method and wet methods.Amine process, N methylpyrrolidone process and arsenic alkaline process etc. in activated carbon method, Claus method and wet desulphurization in conventional dry desulfurization or floor space is large, absorption liquid is poisonous, inflammable, can pollute etc. ocean, all be not suitable for the desulfurizing and purifying of offshore oil production associated gas.LO-CAT method in wet desulphurization and LO-CAT II method are because having the following advantages: (1) solution is made up of carbonate, Complexing Iron etc., cheap and easy to get and nontoxic to marine organisms, can not pollute seawater; (2) absorption and regeneration all can operate at normal temperatures and pressures, and energy consumption is low; (3) desulfuration efficiency is high, can reach 99.99%; (4) integrate desulfurization and sulphur recovery, and sulphur quality is good; (5) applied range, operating flexibility is large, and compact mechanical structure is easy to operate and control, and is considered to more promising sulfur removal technology, can meet the requirement of offshore drilling platform finite volume and high safety factor.
Offshore drilling platform, away from coastline, has high requirement to platform safety.Therefore, the desulfurizing and purifying of offshore drilling platform oil field gas is preferably selected raw material cheap and easy to get in surrounding environment and nonflammable, explosive solvent, the design technology of the little and low-temp low-pressure high safety factor of the desulfurizing agent that ocean is not polluted, floor space.Obviously, utilizing and partly utilize the alkaline desulfurization of natural sea-water is best selection.Therefore, remove the H in offshore oil production associated gas in conjunction with the alkalescence of LO-CAT II sulfur removal technology and seawater in the seawater improvement LO-CAT II method being integrally formed
2s likely has good development prospect.
Summary of the invention
The deficiency existing for prior art, provide a kind of overcome that conventional doctor treatment exists there are to the deficiencies such as poisonous, the inflammable and floor space of potential pollution, doctor solution is large ocean, can meet the technological requirement of offshore production platform finite volume and low-temp low-pressure high safety factor, comply with the sea-changed LO-CAT II method of utilizing of blue ocean expanding economy trend and remove H in offshore oil production associated gas
2the method of S.
For solving the problems of the technologies described above, the technical solution used in the present invention is: one utilizes sea-changed LO-CAT II method to remove H in offshore oil production associated gas
2the method of S, will contain H
2the simulation natural gas of S passes in the redox mediator absorption liquid that adds the seawater of catalyst and complexing agent and be mixed with, and blasts a certain amount of air, as reactor outlet H in absorption liquid simultaneously
2s concentration needs removable parts absorption liquid to continue desulfurization while exceeding index.The absorption liquid of changing filters out after product sulphur, by can be recycled after air regenesis.
Above-mentioned remove H in offshore oil production associated gas
2the method of S, described catalyst is Fe
3+, Fe
3+concentration is 0.0001mol/L-0.005mol/L.
Above-mentioned remove H in offshore oil production associated gas
2the method of S, described complexing agent is one or more the mixture in EDTA (concentration is 0mol/L-0.005mol/L), HEDTA (concentration is 0.0001mol/L-0.002mol/L), D-sorbite (concentration is 0.0001mol/L-0.002mol/L), NTA (concentration is 0mol/L-0.005mol/L).
Above-mentioned remove H in offshore oil production associated gas
2the method of S, described air content is in the air excess factor ε scope that is 10-120.
Above-mentioned remove H in offshore oil production associated gas
2the method of S, described desulfurization is to be to carry out under 6-10 condition in 25 ℃-70 ℃ of temperature and absorption liquid original ph.
Above-mentioned remove H in offshore oil production associated gas
2the method of S, the described doctor solution with air regenesis is changed carries out at normal temperatures and pressures.
The present invention utilizes sea-changed LO-CAT II method to remove H in offshore oil production associated gas
2the advantage of the method for S is: what can overcome that conventional doctor treatment exists has the deficiencies such as poisonous, the inflammable and floor space of potential pollution, doctor solution is large to ocean, can meet the technological requirement of offshore production platform finite volume and low-temp low-pressure high safety factor, comply with blue ocean expanding economy trend.
Accompanying drawing explanation
Fig. 1 is seawater and distilled water preparation absorption liquid desulfurized effect comparison diagram;
Fig. 2 is that temperature is to H
2s conversion ratio affect reference diagram;
Fig. 3 is the affect reference diagram of temperature on time of break-through and liquid phase Sulfur capacity.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further details;
As shown in Figure 1, 2, 3, one utilizes sea-changed LO-CATII method to remove H in offshore oil production associated gas
2the method of S, will contain H
2the natural gas of S, passes into and adds in the redox mediator absorption liquid that the seawater of catalyst and complexing agent is mixed with, and blasts a certain amount of air, as reactor outlet H in absorption liquid simultaneously
2s concentration needs removable parts absorption liquid to continue desulfurization while exceeding index.The absorption liquid of changing filters out after product sulphur, by can be recycled after air regenesis.
Catalyst of the present invention is Fe
3+, complexing agent is one or more the mixture in EDTA (concentration is 0mol/L-0.005mol/L), HEDTA (concentration is 0.0001mol/L-0.002mol/L), D-sorbite (concentration is 0.0001mol/L-0.002mol/L), NTA (concentration is Omol/L-0.005mol/L).Concrete technology operating condition is at Fe
3+concentration is that 0.0001mol/L-0.005mol/L, air excess factor ε are desulfurization under 10-120,25 ℃-70 ℃ of temperature, the absorption liquid original ph condition that is 6-10, passes at normal temperatures and pressures air regenesis.
Embodiment 1:
(1) measure fresh seawater in 2L beaker, and be placed in glass water bath with thermostatic control; (2) take respectively complexing agent
M
eDTA-2Na=0.945g, m
hBDTA: 0.520, m
d-sorbite=0.07g, adds respectively in the beaker that fills seawater, and constantly stirs it is dissolved completely with glass bar; (3) take
add in above-mentioned solution, until completely dissolved, survey its pH value and be acid; (4) in solution, slowly add anhydrous Na
2cO
3and constantly stir, in the time of its pH=8, be made into Absorption by Sea Water liquid.Due to Fe
3+unstable under alkali condition, therefore, Absorption by Sea Water liquid needs matching while using.
Replace seawater with distilled water in addition, according to the step preparation distilled water absorption liquid of (1)-(4).Seawater preparation absorption liquid and the desulphurizing activated evaluation experimental condition of distilled water preparation absorption liquid are as follows: feed gas volume flow v=600ml/min, and 25 ℃ of temperature, absorption liquid original ph is 8,
air excess factor ε be 60 ° of its desulfurized effect contrast and experiment as shown in Figure 1.Under identical operating condition, seawater is prepared H in absorption liquid as seen from Figure 1
2s conversion ratio is than H in distilled water preparation same period absorption liquid
2the conversion ratio of S is slightly high, and H in seawater preparation absorption liquid
2the time of break-through of S is 260min, than H in distilled water preparation absorption liquid
2the time of break-through (200min) of S is slightly long.Therefore, seawater removes H
2s has certain advantage compared with distilled water.Visible sea-changed LO-CAT II method is to H
2s has good removal effect.
Embodiment 2:
(1) measure fresh seawater in 2L beaker, and be placed in glass water bath with thermostatic control; (2) take respectively complexing agent m
eDTA-2Na: 1.23g, m
hEDTA: 0.38g, the moon
d-sorbite: 0.31g, adds respectively in the beaker that fills seawater, and constantly stirs it is dissolved completely with glass bar; (3) take
add in above-mentioned solution, until completely dissolved, survey its pH value and be acid; (4) in solution, slowly add anhydrous Na
2c0
3and constantly stir, in the time of its pH=8, be made into Absorption by Sea Water liquid.The desulphurizing activated evaluation experimental condition of Absorption by Sea Water liquid is as follows: feed gas volume flow v=600ml/min, and absorption liquid original ph is 8,
air excess factor ε is 60.Desulfurized effect under different temperatures as shown in Figures 2 and 3.Can be found out by Fig. 2 and Fig. 3, low temperature is conducive to H
2s removes, H 25 ℃ time
2it is longer that S conversion ratio maintains more than 80% time, can reach 980min, when the time of break-through 25 ℃ time is 55 ℃ 16 times.
Certainly, above-mentioned explanation is not limitation of the present invention, and the present invention is also not limited to above-mentioned giving an example; those skilled in the art; in essential scope of the present invention, variation, remodeling, interpolation or the replacement made, all should belong to protection scope of the present invention.
Claims (6)
1. one kind is utilized sea-changed LO-CAT II method to remove H in offshore oil production associated gas
2the method of S, is characterized in that: will contain H
2the simulation natural gas of S passes in the redox mediator absorption liquid that adds the seawater of catalyst and complexing agent and be mixed with, and blasts a certain amount of air, as reactor outlet H in absorption liquid simultaneously
2s concentration needs removable parts absorption liquid to continue desulfurization while exceeding index.The absorption liquid of changing filters out after product sulphur, by can be recycled after air regenesis.
2. according to claim 1ly remove H in offshore oil production associated gas
2the method of S, is characterized in that: described catalyst is Fe
3+, Fe
3+concentration is 0.0001mol/L-0.005mol/L.
3. according to claim 1ly remove H in offshore oil production associated gas
2the method of S, is characterized in that: described complexing agent is one or more the mixture in EDTA (concentration is O mol/L-0.005mol/L), HEDTA (concentration is 0.0001mol/L-0.002mol/L), D-sorbite (concentration is 0.0001mol/L-0/002mol/L), NTA (concentration is 0 mol/L-0.005mol/L).
4. according to claim 1ly remove H in offshore oil production associated gas
2the method of S, is characterized in that: described air content is in the air excess factor ε scope that is 10-120.
5. according to claim 1ly remove H in offshore oil production associated gas
2the method of S, is characterized in that: described desulfurization is to be to carry out under 6-10 condition in 25 ℃-70 ℃ of temperature and absorption liquid original ph.
6. according to claim 1ly remove H in offshore oil production associated gas
2the method of S, is characterized in that: the described doctor solution with air regenesis is changed carries out at normal temperatures and pressures.
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|---|---|---|---|
| CN201210457932.XA CN103801183A (en) | 2012-11-15 | 2012-11-15 | Method for removing H2S in offshore oil production associated gas by utilizing seawater modified LO-CATII method |
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|---|---|---|---|
| CN201210457932.XA CN103801183A (en) | 2012-11-15 | 2012-11-15 | Method for removing H2S in offshore oil production associated gas by utilizing seawater modified LO-CATII method |
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Application publication date: 20140521 |