CN105771539A - Process for removing high-concentration hydrogen sulfide exhaust applicable to refinery plants - Google Patents
Process for removing high-concentration hydrogen sulfide exhaust applicable to refinery plants Download PDFInfo
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- CN105771539A CN105771539A CN201610193764.6A CN201610193764A CN105771539A CN 105771539 A CN105771539 A CN 105771539A CN 201610193764 A CN201610193764 A CN 201610193764A CN 105771539 A CN105771539 A CN 105771539A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0462—Temperature swing adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1425—Regeneration of liquid absorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1431—Pretreatment by other processes
- B01D53/1437—Pretreatment by adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1468—Removing hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
- B01D2252/20478—Alkanolamines
- B01D2252/20489—Alkanolamines with two or more hydroxyl groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a process for removing high-concentration hydrogen sulfide exhaust applicable to refinery plants and relates to the technical field of gas desulfurization and purification. The process disclosed by the invention has the advantages that after PSA (Pressure Swing Adsorption) concentration, part of gas with rich H2S enters a Claus unit directly, so that the energy consumption of a machine pump is reduced, and simultaneously, the loss of compound amine liquid is reduced; remaining gas can select continuous deep removal of H2S, and according to detection data from a laboratory at present, the content of H2S of the remaining gas subjected to PSA concentration is about 200-300ppm, and simultaneously, the gas content is reduced than before by 20%; and multiple modes such as a chemical absorption method, a temperature swing adsorption method and a pressure swing absorption method can be selected for continuous deep desulfurization.
Description
Technical field
The present invention relates to gas sweetening purification technique field, more particularly to the removing process of a kind of high-concentration hydrogen sulfide tail gas suitable in refinery.
Background technology
Along with industrial expansion, environmental problem is also increasingly severe, and wherein sulphur pollution is one of pollution problem of allowing of no optimist most；Chemical Manufacture is the main path of generation sulphur pollution with sulfur gas combustion, sulphur pollution will be contained, it is necessary to band sulfur fuel gas in Chemical Manufacture is carried out desulfurization process.
Such as Fig. 2, in existing gas sweetening technology, generally first pass around chemical absorption method, all gas is passed in absorption liquid, by H2S absorbs in solution, and by delivering to Cross unit after hot recycling, residual gas enters back into fine de-sulfur link；And in actual production, produce and arrived certain scale, it is necessary to the tolerance of process is huge, then the circular flow of the chemical solvent of needs also becomes big accordingly, drives the energy consumption that chemical solvent circulates to uprise accordingly；Mass air flow can take away part chemical solvent simultaneously, causes chemical solvent to lose, adds cost for desulfurization workshop section in turn.
Summary of the invention
The present invention provides the removing process of a kind of high-concentration hydrogen sulfide tail gas suitable in refinery, first carries out pressure-variable adsorption sub-argument and goes out portioned product gas, reduces deep removal H2The tolerance of S technique, desorbing obtains the hydrogen sulfide gas of concentration, is routed directly to Cross unit, solves owing to the large-minded chemical solvent circular flow caused is big, loss is big, energy consumption is high, the problem of long flow path.
For solving above-mentioned technical problem, the present invention by the following technical solutions:
The removing process of a kind of high-concentration hydrogen sulfide tail gas suitable in refinery, comprises the steps:
A. the hydrogen sulphide concentration stage, unstrpped gas enters pressure swing adsorption system through admission line, by pressure-variable adsorption unstripped gas is divided into the middle gas containing a small amount of hydrogen sulfide and rich hydrogen sulfide stripping gas two parts, described middle gas is stripped of most hydrogen sulfide, sulfur content is low, described rich hydrogen sulfide stripping gas is directly entered Cross unit, reclaims；
B. the deep removal hydrogen sulfide stage, the hydrogen sulfide in middle gas is continued deep removal.
Further, the described deep removal hydrogen sulfide stage adopts the mode of chemical absorbing to remove hydrogen sulfide, centre gas is passed in pressurizing desulfurizing liquid ejector, middle gas is made to be fully contacted with chemical solvent, chemical solvent is made to fully absorb the hydrogen sulfide in middle gas, absorbing enters in serotonin liquid/gas separator after completely, the gas product of deep removal hydrogen sulfide is produced, rich hydrogen sulfide containing amine liquid goes to amine liquid regenerator through serotonin rich solution pump, the hydrogen sulfide of absorption is departed from and is back in pressure swing adsorption system, amine lean solution returns back to serotonin liquid/gas separator through serotonin lean pump, serotonin liquid circulates in systems through serotonin liquid circulating pump.
Further, described serotonin liquid is methyl diethanolamine liquid, uses methyl diethanolamine liquid to have the advantages that solvent loss is few, regeneration temperature is low, and compared to other serotonin liquid, methyl diethanolamine liquid is comparatively thorough to the absorption of hydrogen sulfide.
Further, the described deep removal hydrogen sulfide stage adopts the mode of Temp .-changing adsorption to carry out elimination hydrogen sulfide, and centre gas is passed into temperature swing adsorption system, and after room temperature absorption completely, gas product produces, and the stripping gas obtained after intensification desorbing is back in pressure swing adsorption system.
Further, the described deep removal hydrogen sulfide stage still adopts the mode of pressure-variable adsorption to carry out elimination hydrogen sulfide, centre gas is passed into next section of pressure swing adsorption system, the completely rear gas product of High Pressure Absorption produces, and the stripping gas obtained after low pressure desorbing is back in the pressure swing adsorption system in hydrogen sulphide concentration stage.
Compared with prior art, the invention has the beneficial effects as follows:
(1) make low pressure containing H by pressure-variable adsorption2H in S tail gas2S concentrates, and a step reaches to reclaim H2The requirement of S device, effectively reduces next step deep removal H2The load of S technique, thus reducing energy consumption and the material consumption of whole desulfurizer；
(2) first carry out pressure-variable adsorption sub-argument and go out portioned product gas, reduce deep removal H2The tolerance of S technique, decreases the loss of serotonin liquid.
Accompanying drawing explanation
Fig. 1 is the process chart of the embodiment of the present invention 1；
Fig. 2 is the process chart of the embodiment of the present invention 2；
Fig. 3 is the process chart of the embodiment of the present invention 3；
Fig. 4 is prior art processes flow chart；
Figure acceptance of the bid note is respectively as follows: 1, admission line；2, pressurizing desulfurizing liquid ejector；3, amine liquid withdrawer；4, serotonin liquid/gas separator；5, serotonin liquid cooler；6, serotonin liquid circulating pump；7, serotonin rich solution pump；8, amine liquid regenerator；9, serotonin lean pump；11, adsorption tower；12, resolution gas surge tank；13, resolution gas booster fan；14, jet chimney；15, temperature swing absorption unit.
Detailed description of the invention
The application principle of the present invention, effect and effect, be explained by following embodiment.
Embodiment 1
As it is shown in figure 1, the removing process of a kind of high-concentration hydrogen sulfide tail gas suitable in refinery, comprise the steps:
A. the hydrogen sulphide concentration stage, unstrpped gas enters the adsorption tower 11 in pressure swing adsorption system through admission line 1, by pressure-variable adsorption unstripped gas is divided into the middle gas containing a small amount of hydrogen sulfide and rich hydrogen sulfide stripping gas two parts, described middle gas is stripped of most hydrogen sulfide, sulfur content is low, described rich hydrogen sulfide stripping gas enters entrance Cross unit after resolution gas booster fan 13 supercharging through resolution gas surge tank 12, reclaims；
B. the deep removal hydrogen sulfide stage, hydrogen sulfide in middle gas is continued deep removal, the mode that methyl diethanolamine liquid absorbs hydrogen sulfide is adopted to remove hydrogen sulfide, centre gas is passed in pressurizing desulfurizing liquid ejector 2, middle gas is made to be fully contacted with methyl diethanolamine liquid, methyl diethanolamine liquid fully absorbs the hydrogen sulfide in middle gas, absorbing enters in methyl diethanolamine liquid/gas separator after completely, the gas product of deep removal hydrogen sulfide is produced, rich hydrogen sulfide containing amine liquid goes to amine liquid regenerator through methyl diethanolamine rich solution pump, the hydrogen sulfide of absorption is departed from and is back in pressure swing adsorption system, amine lean solution returns back to methyl diethanolamine liquid/gas separator through methyl diethanolamine lean pump, methyl diethanolamine liquid circulates in systems through methyl diethanolamine liquid circulating pump, ensure the recycling of methyl diethanolamine liquid.
In the present embodiment, in unstripped gas hydrogen sulfide at concentrations up to more than 2%, being operated by pressure is that about 0.2MPa, operation temperature are maintained at the pressure-variable adsorption effect concentrating and separating of 80 ~ 140 DEG C and go out purer hydrogen, makes containing H2H in the resolution gas of S2S concentration reaches the entrance concentration requirement of Cross unit, directly stripping gas is sent into Cross unit and recycles, according to the detection data in current laboratory, and the H of residual gas after PSA concentrates2S content is about 200～300ppm, and tolerance at least reduced 20% relatively originally simultaneously, and another part is containing trace H2The gas of S then continues demethyl diethanolamine liquid absorption section deep removal H2S, relatively prior art, required methyl diethanolamine liquid measure at least reduces 20%, and corresponding energy consumption reduces；The present embodiment makes low pressure containing H by pressure-variable adsorption2H in S tail gas2S concentrates, and a step reaches to reclaim H2The requirement of S device, effectively reduces next step deep removal H2The load of S technique, thus reducing energy consumption and the material consumption of whole desulfurizer.
Embodiment 2
As in figure 2 it is shown, the removing process of a kind of high-concentration hydrogen sulfide tail gas suitable in refinery, comprise the steps:
A. the hydrogen sulphide concentration stage, unstrpped gas enters pressure swing adsorption system through admission line 1, by pressure-variable adsorption unstripped gas is divided into the middle gas containing a small amount of hydrogen sulfide and rich hydrogen sulfide stripping gas two parts, described middle gas is stripped of most hydrogen sulfide, sulfur content is low, described rich hydrogen sulfide stripping gas enters entrance Cross unit after resolution gas booster fan 13 supercharging through resolution gas surge tank 12, reclaims；
B. the deep removal hydrogen sulfide stage, hydrogen sulfide in middle gas is continued deep removal, the mode adopting Temp .-changing adsorption removes hydrogen sulfide, centre gas is passed in temperature swing absorption unit 2, after room temperature absorption completely, gas product produces temperature swing absorption unit 2, and after intensification desorbing, stripping gas is back in pressure swing adsorption system.
In the present embodiment, in unstripped gas hydrogen sulfide at concentrations up to more than 2%, being operated by pressure is that about 0.2MPa, operation temperature are maintained at the pressure-variable adsorption effect concentrating and separating of 80 ~ 140 DEG C and go out purer hydrogen, makes containing H2H in the resolution gas of S2S concentration reaches the entrance concentration requirement of Cross unit, directly stripping gas is sent into Cross unit and recycles, according to the detection data in current laboratory, and the H of residual gas after PSA concentrates2S content is about 200～300ppm, and tolerance reduced 20% more originally simultaneously, and another part is containing trace H2The gas of S then continues temperature swing absorption unit deep removal H2S, Temp .-changing adsorption is in conjunction with pressure-variable adsorption, and getable purity of product gas is high, is suitable for purity of product gas is required big production technology；The present embodiment makes low pressure containing H by pressure-variable adsorption2H in S tail gas2S concentrates, and a step reaches to reclaim H2The requirement of S device, effectively reduces next step deep removal H2The load of S technique, thus reducing energy consumption and the material consumption of whole desulfurizer.
Embodiment 3
As it is shown on figure 3, the removing process of a kind of high-concentration hydrogen sulfide tail gas suitable in refinery, comprise the steps:
A. the hydrogen sulphide concentration stage, unstrpped gas enters pressure swing adsorption system through admission line 1, by pressure-variable adsorption unstripped gas is divided into the middle gas containing a small amount of hydrogen sulfide and rich hydrogen sulfide stripping gas two parts, described middle gas is stripped of most hydrogen sulfide, sulfur content is low, described rich hydrogen sulfide stripping gas enters entrance Cross unit after resolution gas booster fan 13 supercharging through resolution gas surge tank 12, reclaims；
B. the deep removal hydrogen sulfide stage, the mode of pressure-variable adsorption is still adopted to carry out elimination hydrogen sulfide in the hydrogen sulfide in middle gas, centre gas is passed into next section of pressure swing adsorption system, the completely rear gas product of High Pressure Absorption produces, and the stripping gas obtained after low pressure desorbing is back in the pressure swing adsorption system in hydrogen sulphide concentration stage.
In the present embodiment, in unstripped gas hydrogen sulfide at concentrations up to more than 2%, be operated by pressure be about 0.2MPa, operation temperature is maintained at the pressure-variable adsorption effect of 80 ~ 140 DEG C makes containing H2H in the resolution gas of S2S concentration reaches the entrance concentration requirement of Cross unit, directly stripping gas is sent into Cross unit and recycles, and another part is containing trace H2The gas of S then continues next stage pressure swing adsorption apparatus deep removal H2S, two sections of pressure-variable adsorptions, obtain the gas product that purity is more than 99.9%, general production technology can be substantially met；The present embodiment makes low pressure containing H by pressure-variable adsorption2H in S tail gas2S concentrates, and a step reaches to reclaim H2The requirement of S device, effectively reduces next step deep removal H2The load of S technique, thus reducing energy consumption and the material consumption of whole desulfurizer.
It is embodiments of the invention as mentioned above.The present invention is not limited to above-mentioned embodiment, and anyone should learn the structure change made under the enlightenment of the present invention, and every have same or like technical scheme with the present invention, each falls within protection scope of the present invention.
Claims (5)
1. the removing process of the high-concentration hydrogen sulfide tail gas being applicable to refinery, it is characterised in that comprise the steps:
The hydrogen sulphide concentration stage, unstrpped gas enters pressure swing adsorption system through admission line, by pressure-variable adsorption unstripped gas is divided into the middle gas containing a small amount of hydrogen sulfide and rich hydrogen sulfide stripping gas two parts, described middle gas is stripped of most hydrogen sulfide, sulfur content is low, described rich hydrogen sulfide stripping gas is directly entered Cross unit, reclaims；
In the deep removal hydrogen sulfide stage, the hydrogen sulfide in middle gas is continued deep removal.
2. the removing process of a kind of high-concentration hydrogen sulfide tail gas suitable in refinery as claimed in claim 1, it is characterized in that, the described deep removal hydrogen sulfide stage adopts the mode of chemical absorbing to remove hydrogen sulfide, centre gas is passed in pressurizing desulfurizing liquid ejector, middle gas is made to be fully contacted with chemical solvent, chemical solvent fully absorbs the hydrogen sulfide in middle gas, absorbing enters in serotonin liquid/gas separator after completely, the gas product of deep removal hydrogen sulfide is produced, rich hydrogen sulfide containing amine liquid goes to amine liquid regenerator through serotonin rich solution pump, the hydrogen sulfide of absorption is departed from and is back in pressure swing adsorption system, amine lean solution returns back to serotonin liquid/gas separator through serotonin lean pump, serotonin liquid circulates in systems through serotonin liquid circulating pump.
3. the removing process of a kind of high-concentration hydrogen sulfide tail gas suitable in refinery as claimed in claim 2, it is characterised in that described serotonin liquid is methyl diethanolamine liquid.
4. the removing process of a kind of high-concentration hydrogen sulfide tail gas suitable in refinery as claimed in claim 1, it is characterized in that, the described deep removal hydrogen sulfide stage adopts the mode of Temp .-changing adsorption to carry out elimination hydrogen sulfide, centre gas is passed into temperature swing adsorption system, after room temperature absorption completely, gas product produces, and the stripping gas obtained after intensification desorbing is back in pressure swing adsorption system.
5. the removing process of a kind of high-concentration hydrogen sulfide tail gas suitable in refinery as claimed in claim 1, it is characterized in that, the described deep removal hydrogen sulfide stage still adopts the mode of pressure-variable adsorption to carry out elimination hydrogen sulfide, centre gas is passed into next section of pressure swing adsorption system, the completely rear gas product of High Pressure Absorption produces, and the stripping gas obtained after low pressure desorbing is back in the pressure swing adsorption system in hydrogen sulphide concentration stage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610193764.6A CN105771539A (en) | 2016-03-31 | 2016-03-31 | Process for removing high-concentration hydrogen sulfide exhaust applicable to refinery plants |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610193764.6A CN105771539A (en) | 2016-03-31 | 2016-03-31 | Process for removing high-concentration hydrogen sulfide exhaust applicable to refinery plants |
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| CN105771539A true CN105771539A (en) | 2016-07-20 |
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| CN201610193764.6A Pending CN105771539A (en) | 2016-03-31 | 2016-03-31 | Process for removing high-concentration hydrogen sulfide exhaust applicable to refinery plants |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040073076A1 (en) * | 2002-10-10 | 2004-04-15 | Drnevich Raymond Francis | Integrated olefin recovery and hydrogen production from refinery off-gases |
| CN102597671A (en) * | 2009-11-02 | 2012-07-18 | 埃克森美孚上游研究公司 | Cryogenic system for removing acid gases from a hydrocarbon gas stream, with removal of hydrogen sulfide |
| CN102626580A (en) * | 2011-02-02 | 2012-08-08 | 何巨堂 | Two-step pressure swing adsorption separation method of multicomponent gas containing hydrogen and hydrogen sulfide |
| CN104815530A (en) * | 2015-05-06 | 2015-08-05 | 四川天采科技有限责任公司 | Jet-type membrane-filtering fine-desulfuration device suitable for refinery plant |
| CN104845671A (en) * | 2015-04-27 | 2015-08-19 | 宁夏宝塔石化科技实业发展有限公司 | Novel process technology using combined operation mode |
-
2016
- 2016-03-31 CN CN201610193764.6A patent/CN105771539A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040073076A1 (en) * | 2002-10-10 | 2004-04-15 | Drnevich Raymond Francis | Integrated olefin recovery and hydrogen production from refinery off-gases |
| CN102597671A (en) * | 2009-11-02 | 2012-07-18 | 埃克森美孚上游研究公司 | Cryogenic system for removing acid gases from a hydrocarbon gas stream, with removal of hydrogen sulfide |
| CN102626580A (en) * | 2011-02-02 | 2012-08-08 | 何巨堂 | Two-step pressure swing adsorption separation method of multicomponent gas containing hydrogen and hydrogen sulfide |
| CN104845671A (en) * | 2015-04-27 | 2015-08-19 | 宁夏宝塔石化科技实业发展有限公司 | Novel process technology using combined operation mode |
| CN104815530A (en) * | 2015-05-06 | 2015-08-05 | 四川天采科技有限责任公司 | Jet-type membrane-filtering fine-desulfuration device suitable for refinery plant |
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Application publication date: 20160720 |