CN102952589A - Method for removing acid gas out of raw gas or shifted gas of raw gas - Google Patents
Method for removing acid gas out of raw gas or shifted gas of raw gas Download PDFInfo
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- CN102952589A CN102952589A CN2012104119307A CN201210411930A CN102952589A CN 102952589 A CN102952589 A CN 102952589A CN 2012104119307 A CN2012104119307 A CN 2012104119307A CN 201210411930 A CN201210411930 A CN 201210411930A CN 102952589 A CN102952589 A CN 102952589A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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Abstract
The invention provides a method for removing acid gas out of raw gas or shifted gas of raw gas. The method is characterized in that because water content of recycled methanol can be strictly controlled, the corrosion of the wet acid gas to equipment is lightened or avoided, and the service life of the equipment is prolonged; and the heat transfer heat resistance of a heat exchanger is reduced, so that the refrigeration capacity is saved and the purposes of saving energy and reducing emission are reached. The method is also characterized in that gas treated by a Claus catalyst bed layer in a Claus sulfur recycling device is recycled, wherein above 90 percent of hydrogen sulfide contained in the gas is recycled in the form of liquid sulfur, and exhausted tail gas (containing less than 10 percent of residual hydrogen sulfide) is treated through a process, and is sent to a lower column of hydrogen sulfide concentration tower of a low-temperature methanol washing device to be treated, so that chemical sulfur in the Claus acid tail gas is absorbed by recycled methanol. Therefore, the tail gas treatment procedure in the Claus sulfur recycling device is simplified and the zero emission of acid tail gas is realized.
Description
Technical field
The present invention relates to a kind of removal methods of the conversion gas sour gas for raw gas or raw gas, belong to acid gas removal method and technology field.
Background technology
In the existing coal chemical engineering equipment, its raw gas (or raw gas resulting conversion gas after conversion, hereinafter to be referred as conversion gas) the removing of institute's acid gas-containing, adopt " low-temperature rectisol method " to purify to be generally acknowledged it is the most effective, most economical and the most energy-conservation method by the home and abroad.
In the process that raw gas is cleaned, with the sour gas in methyl alcohol (entering the poor methanol on absorption tower) the absorption raw gas of low temperature, it has absorbed the rich methanol that cries of sour gas.Rich methanol is carried and process such as heat regeneration etc. is emitted the sour gas that absorbs and become and be poor methanol through thermal exchange, decompression, nitrogen.Poor methanol through pressurization, carry out the exchange of heat with rich methanol again and recycle,---desorb---absorbs---the again working cycle of desorb more namely to have finished absorption.
Because coal chemical engineering equipment is a very complicated apparatus, comprise that namely a lot of height devices consist of a factory, and the refining plant of raw gas (or conversion gas) sub-device in the complicated coal chemical engineering equipment just.
The sub-device of technique in the factory or other all can cause the parking of " low temperature washing device for methanol " such as arbitrary the breaking down of the sub-device of general facilities.The parking of " low temperature washing device for methanol " and again driving are the reasons that causes the increase of water-content in the recycle methanol.
The design load of water-content is in the recycle methanol :≤0.5% (Wt%), this moment, system was without corrosion.Water-content is in recycle methanol :≤1.0% (Wt%), and system has slight corrosion; Water-content is in the recycle methanol :≤2.0% (Wt%), and system has obvious corrosion; Water-content is in the recycle methanol :≤5.0% (Wt%), system has heavy corrosion.
For this reason, for the long-term operation of keeping factory and energy-saving and cost-reducing, water-content can be stabilized in design load in must strict controlled circulation methyl alcohol, that is to say: in case exceeding standard appears in water-content in the recycle methanol, must very fast it be lowered, occur with the corrosion of stopping or reduce rapidly equipment and pipeline.But existing low temperature washing device for methanol is to control and the effective control device of stable shortage of water-content in the recycle methanol.
Summary of the invention
The objective of the invention is in order to solve existing method to the control of water-content in the recycle methanol and the stable problem that lacks effective control device, and then a kind of removal methods of the conversion gas sour gas for raw gas or raw gas is provided.
The objective of the invention is to be achieved through the following technical solutions:
A kind of removal methods of the conversion gas sour gas for raw gas or raw gas comprises: one, with the methyl alcohol of low temperature, absorb the sour gas in raw gas or the conversion gas, its poor methanol that has absorbed sour gas is rich methanol; Two, rich methanol through thermal exchange, reduce pressure, enter CO
2The product tower, cat head obtains CO
2Product, CO after the re-heat
2Send into urea plant; Three, rich methanol continues decompression and arrives H
2The S upgrading tower, H
2The epimere of S upgrading tower is H
2The again absorber portion of S+COS, H
2The hypomere of S upgrading tower is the nitrogen stripping section, from H
2The concentrated cat head of S is drawn tail gas, enters atmosphere after the re-heat; Four, from H
2The rich methanol that S upgrading tower epimere is drawn is the minimum temperature in the system, its first with the poor methanol that comes self-heating regenerator column still change cold, the rich methanol of drawing with the self-absorption tower again change cold after, import CO
2The lower tower of product tower finally is to import H
2The nitrogen stripping section of S upgrading tower hypomere; The rich methanol of five, drawing from the nitrogen stripping section send hot regenerator column after heat exchange, hot regeneration overhead escaping gas is contained (H after water-cooled, ammonia are cold
2S+COS)+CO
2+ N
2Sour gas, described sour gas is fed to claus sulphur recovery units; Six, most Extract of hot regenerator column, namely poor methanol continues circulation to the absorption tower and absorbs after pump and precooling; Small part then is admitted to the methanol/water knockout tower as feeding liquid; Seven, intrinsic methanol/water knockout tower only has two bursts of chargings, the Extract of one instant heating regenerator column; It two is the separation liquid phase of feeding gas separator; Eight, send the pure methyl alcohol that comes self-heating regeneration overhead separator a part to hot regenerator column with pump pressure, another part is to the methanol/water knockout tower, and respectively as the trim the top of column liquid of hot regenerator column and methanol/water knockout tower; Nine, the Exhaust Gas of hot regeneration overhead is sent to claus sulphur recovery units and makes unstripped gas, and it is laggard to secondary or three grades of claus catalyst beds through heating that unstripped gas is allocated into stoichiometric air, at the claus catalyst bed claus reaction occurs; Ten, reacted gas is through cooling, condensation and enter and be separated into gas, liquid two-phase in the separator, and liquid phase is: the liquid Sulfur; Gas phase is: the oxidizing gas that contains H2S, COS and free oxygen, this oxidizing gas is through being heated to the active temperature of Co-Mo hydrogenation catalyst (or hydrolyst), and is sent in the reactor that Co-Mo hydrogenation catalyst (or hydrolyst) is housed; 11, in described reactor, oxidizing gas is reduced, i.e. SO
2, COS is reduced into H
2S, free oxygen then are hydrogenated into water; Described reducing gas again through just cold, dehydrate and eventually cold after, deliver to the H of low temperature washing device for methanol
2The nitrogen stripping section of tower under the S upgrading tower; At H
2The lower tower of S upgrading tower is absorbed by the recycle methanol that flows down since upper tower, and the recycle methanol that has absorbed sour gas is then drawn at the bottom of tower, is pressed to hot regenerator column after re-heat; 12, the mixing sour gas of hot regeneration overhead discharge is sent to again claus sulphur recovery units through cooling, condensation with after separating again, in claus sulphur recovery units, mix sour gas after secondary or three grades of claus catalyst beds reactions, be separated through cooling and two, liquid phase is: the liquid Sulfur, gas phase is: contain SO
2Oxidizing gas; 13, oxidizing gas is heated, Heating temperature is 200 ± 5 ℃, and pressure is 0.04Mpa and delivers in the reactor (or hydrolyst) that the Co-Mo hydrogenation catalyst is housed, and the SO in the oxidizing gas
2, COS is reduced into H
2S, free oxygen is reduced into water, is H at last
2S+H
2The gas mixture of O+ indifferent gas; 14, H
2S+H
2The gas mixture of O+ indifferent gas, again through cold at the beginning of 0 ± 5 ℃, dehydrate, 0.45Mpa pressurization and cold eventually after, final cooling temperature is-33 ± 5 ℃, pressure is 0.40Mpa, turns back to heavily again low temperature washing device for methanol H
2The lower tower of S upgrading tower, and the recycle methanol that is flowed down from tower top absorption, the recycle methanol that Zi Tadi draws is sent to hot regenerator column through heating, so realizes cyclical operation.
The present invention has the following advantages: therefore method of the present invention makes prolong the work-ing life of equipment owing to strictly controlled the water-content in the recycle methanol.The minimizing of corrosion is so that the heat exchange thermal resistance of the interchanger in the flow process reduces in addition, and heat transfer temperature difference reduces, and refrigerating capacity is saved, and has reached energy-saving and cost-reducing purpose.
In addition, the present invention has not only simplified the flow process of exhaust treatment system in the claus sulphur recovery units widely, can also make acid tail gas reach " zero release ", is the good method of satisfactory to both parties neat U.S..
Embodiment
The below will the present invention is described in further detail: present embodiment is implemented under take technical solution of the present invention as prerequisite, has provided detailed embodiment, but protection scope of the present invention is not limited to following embodiment.
The removal methods of a kind of conversion gas sour gas for raw gas or raw gas that present embodiment is related, comprise: the methyl alcohol of one, using low temperature, (namely entering to absorb the poor methanol of cat head) absorbs the sour gas in raw gas or the conversion gas, and its poor methanol that has absorbed sour gas is rich methanol; Two, rich methanol through thermal exchange, reduce pressure, enter CO
2The product tower, cat head obtains CO
2Product, CO after the re-heat
2Send into urea plant; Three, rich methanol continues decompression and arrives H
2The S upgrading tower, H
2The epimere of S upgrading tower is H
2The again absorber portion of S+COS, H
2The hypomere of S upgrading tower is the nitrogen stripping section, from H
2The concentrated cat head of S is drawn tail gas, enters atmosphere after the re-heat; Four, from H
2The rich methanol that S upgrading tower epimere is drawn is the minimum temperature in the system, its first with the poor methanol that comes self-heating regenerator column still change cold, the rich methanol of drawing with the self-absorption tower again change cold after, import CO
2The lower tower of product tower finally is to import H
2The nitrogen stripping section of S upgrading tower hypomere; The rich methanol of five, drawing from the nitrogen stripping section send hot regenerator column after heat exchange, hot regeneration overhead escaping gas is contained (H after water-cooled, ammonia are cold
2S+COS)+CO
2+ N
2Sour gas, described sour gas is fed to claus sulphur recovery units; Six, most Extract of hot regenerator column, namely poor methanol continues circulation to the absorption tower and absorbs after pump and precooling; Small part is admitted to the methanol/water knockout tower as feeding liquid; Seven, the methanol/water knockout tower in the former low temperature washing device for methanol has two bursts of chargings, the Extract of one instant heating regenerator column; It two is the separation liquid phase of feeding gas separator; Eight, the pure methyl alcohol that comes self-heating regeneration overhead separator (i.e. 100% methyl alcohol), send a part to hot regenerator column with pump pressure, another part is to the methanol/water knockout tower, and respectively as the trim the top of column liquid as hot regenerator column and methanol/water knockout tower; Nine, the Exhaust Gas of hot regeneration overhead is sent to claus sulphur recovery units and makes unstripped gas, and it is laggard to secondary or three grades of claus catalyst beds through heating that unstripped gas is allocated into stoichiometric air, at the claus catalyst bed claus reaction occurs; Ten, reacted gas is through cooling, condensation and enter and be separated into gas, liquid two-phase in the separator, and liquid phase is: the liquid Sulfur; Gas phase is: oxidisability (contains S0
2, COS and free oxygen etc.) gas, this oxidizing gas is through being heated to the active temperature of Co-Mo hydrogenation catalyst (or hydrolyst), and is sent in the reactor that Co-Mo hydrogenation catalyst (or hydrolyst) is housed; 11, in described reactor, oxidizing gas is reduced, i.e. SO
2, COS is reduced into H
2S, free oxygen then are hydrogenated into water; Described reducing gas again through just cold, dehydrate and eventually cold after, deliver to the H of low temperature washing device for methanol
2The nitrogen stripping section of tower under the S upgrading tower; At H
2The lower tower of S upgrading tower is absorbed by the recycle methanol that flows down since upper tower, and the recycle methanol that has absorbed sour gas is then drawn at the bottom of tower, is pressed to hot regenerator column after re-heat; 12, the hot regeneration overhead mixing sour gas of discharging (comprise in the sour gas and claus sulphur recovery units in the feeding gas that newly enters low temperature washing device for methanol, unconverted H
2The gas two portions such as S (≤10%)) after cooling, separation and re-heat, be sent to again again claus sulphur recovery units, in claus sulphur recovery units, mix sour gas after secondary or three grades of claus catalyst beds reactions, be separated through cooling and two, liquid phase is: the liquid Sulfur, gas phase is: contain SO
2, COS and free oxygen oxidizing gas (temperature: about 170 ℃; Pressure: 0.04Mpa (G)); 13, oxidizing gas is heated, Heating temperature is 200 ± 5 ℃ (active temperatures that depend on Co-Mo hydrogenation catalyst or hydrolyst); Pressure is 0.04Mpa (G)) and deliver in the reactor that Co-Mo hydrogenation catalyst or hydrolyst are housed, and the SO in the oxidizing gas
2, COS is reduced into H2S, free oxygen is reduced into water, and is final for containing H
2S+H
2The gas mixture of O+ indifferent gas; 14, H
2S+H
2The gas mixture of O+ indifferent gas again through cold at the beginning of 0 ± 5 ℃, dehydrate, 0.45Mpa pressurization and cold eventually after, final cooling temperature is-33 ± 5 ℃, pressure is 0.40Mpa, delivers to heavily again low temperature washing device for methanol H
2The lower tower of S upgrading tower (being the nitrogen stripping section), and the recycle methanol that is flowed down from tower top absorption, the recycle methanol that Zi Tadi draws is sent to hot regenerator column through heating, so realizes cyclical operation.
The tower top temperature of described methanol/water knockout tower is 85～95 ℃, the tower temperature that enters of trim the top of column liquid is 35～45 ℃, the temperature of taking self-heating regenerator column tower bottoms is 65～75 ℃, methanol/water liquidus temperature from the feeding gas separator is 46～55 ℃, and the tower reactor temperature of methanol/water knockout tower is 126～136 ℃; The cat head working pressure of described methanol/water knockout tower is 0.24～0.3Mpa, and the tower reactor working pressure is 0.25～0.31Mpa.
When the present invention makes the trim the top of column liquid of methanol/water knockout tower with anhydrous methanol, along with the increase of trim the top of column amount, just may greatly reduce the water content of methanol/water knockout tower cat head evolving gas, very cause in can be anhydrous.The circulation of moisture between methanol/water knockout tower and hot regenerator column namely can not occur again, thereby can make soon the water-content in the recycle methanol drop to design load.
The present invention is unconverted H
2The gases such as S (≤10%) send back to the H of " low temperature washing device for methanol " again
2Again being recycled methyl alcohol in the S upgrading tower absorbs.Thereby, in " claus sulphur recovery units ", do not need again newly-built not only complicated, investment but also high exhaust treatment system, both simplify operation, reduced the investment of factory, reach again and contain H
2" zero release " of S tail gas reduces the pollution to ambient atmosphere.
The above; only be the better embodiment of the present invention; these embodiments all are based on the different implementations under the general idea of the present invention; and protection scope of the present invention is not limited to this; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (2)
1. a removal methods that is used for the conversion gas sour gas of raw gas or raw gas is characterized in that, one, with the methyl alcohol of low temperature, absorb the sour gas in raw gas or the conversion gas, and its poor methanol that has absorbed sour gas is rich methanol; Two, rich methanol through thermal exchange, reduce pressure, enter CO
2The product tower, cat head obtains CO
2Product, CO after the re-heat
2Send into urea plant; Three, rich methanol continues decompression and arrives H
2The S upgrading tower, H
2The epimere of S upgrading tower is H
2The again absorber portion of S+COS, H
2The hypomere of S upgrading tower is the nitrogen stripping section, from H
2The concentrated cat head of S is drawn tail gas, enters atmosphere after the re-heat; Four, from H
2The rich methanol that S upgrading tower epimere is drawn is the minimum temperature in the system, its first with the poor methanol that comes self-heating regenerator column still change cold, the rich methanol of drawing with the self-absorption tower again change cold after, import CO
2The lower tower of product tower finally imports H
2The nitrogen stripping section of S upgrading tower hypomere; The rich methanol of five, drawing from the nitrogen stripping section send hot regenerator column after heat exchange, hot regeneration overhead escaping gas is contained (H after water-cooled, ammonia are cold
2S+COS)+CO
2+ N
2Sour gas, and be fed to claus sulphur recovery units; Six, the Extract of hot regenerator column, i.e. poor methanol, the overwhelming majority is sent and is given through pump pressure and continues the circulation absorption to the absorption tower after cold; Small part then is admitted to the methanol/water knockout tower as feeding liquid; Seven, the methanol/water knockout tower has two bursts of chargings, the Extract of one instant heating regenerator column; It two is the separation liquid phase of feeding gas separator; Eight, the pure methyl alcohol that comes self-heating regeneration overhead separator and send with pump pressure except a part is still delivered to hot regenerator column, another part is then delivered to the methanol/water knockout tower, and as trim the top of column liquid; Nine, the Exhaust Gas of hot regeneration overhead is after cooling, condensation and separating, be sent to claus sulphur recovery units and make unstripped gas, it is laggard to secondary or three grades of claus catalyst beds through heating that unstripped gas is allocated into stoichiometric air, at the claus catalyst bed claus reaction occurs; Ten, reacted gas is through cooling, condensation and enter and be separated into gas, liquid two-phase in the separator, and liquid phase is: the liquid Sulfur; Gas phase is: contain the oxidizing gas of chemical sulphur, behind the active temperature of this oxidizing gas through being heated to the Co-Mo hydrogenation catalyst, deliver in the reactor that the Co-Mo hydrogenation catalyst is housed again; 11, in described reactor, oxidizing gas is reduced, i.e. SO
2Be reduced into H
2S, COS are reduced into H
2S, free oxygen then are hydrogenated into water; Described reducing gas again through just cold, dehydrate and eventually cold after, be sent to again the H of low temperature washing device for methanol
2The nitrogen stripping section of tower under the S upgrading tower; Described reducing gas is at H
2The lower tower of S upgrading tower is absorbed by the recycle methanol that flows down since upper tower, and recycle methanol is then drawn at the bottom of tower, is pressed to hot regenerator column after the re-heat; 12, the mixing sour gas of hot regeneration overhead discharge is sent to again claus sulphur recovery units through cooling, condensation with after separating.In claus sulphur recovery units, mix sour gas after secondary or three grades of claus catalyst beds reactions, be separated through cooling and two, liquid phase is: the liquid Sulfur, gas phase is: contain SO
2, COS and free oxygen oxidizing gas; 13, oxidizing gas is heated, Heating temperature is about: 200 ± 5 ℃, pressure is: 0.04Mpa also delivers in the reactor that Co-Mo hydrogenation catalyst or hydrolyst are housed, and the SO in the oxidizing gas
2, COS and free oxygen be reduced into H
2S+H
2The O+ indifferent gas; 14, H
2S+H
2The O+ indifferent gas again through cold at the beginning of 0 ± 5 ℃, dehydrate, 0.45Mpa pressurization and cold eventually after, final cooling temperature is-33 ± 5 ℃, pressure is 0.40Mpa, delivers to heavily again low temperature washing device for methanol H
2The lower tower of S upgrading tower, and the recycle methanol that is flowed down from tower top absorption, the recycle methanol that Zi Tadi draws is sent to hot regenerator column through heating, so realizes cyclical operation.
2. the removal methods of the conversion gas sour gas for raw gas or raw gas according to claim 1, it is characterized in that, the tower top temperature of described methanol/water knockout tower is 85～95 ℃, the tower temperature that enters of newly-increased trim the top of column liquid is 35～45 ℃, the temperature of taking self-heating regenerator column tower bottoms is 65～75 ℃, methanol/water liquidus temperature from the feeding gas separator is 46～55 ℃, and the tower reactor temperature of methanol/water knockout tower is 126～136 ℃; The cat head working pressure of methanol/water knockout tower is 0.24～0.3Mpa, and the tower reactor working pressure is 0.25～0.31Mpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104119307A CN102952589A (en) | 2012-10-25 | 2012-10-25 | Method for removing acid gas out of raw gas or shifted gas of raw gas |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104119307A CN102952589A (en) | 2012-10-25 | 2012-10-25 | Method for removing acid gas out of raw gas or shifted gas of raw gas |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103446859A (en) * | 2013-09-12 | 2013-12-18 | 中国海洋石油总公司 | Treatment method of acid gases in coal-made natural gas |
| CN106701211A (en) * | 2015-11-12 | 2017-05-24 | 林德股份公司 | Method and device for the selective desulfurization of synthesis gas |
| CN113415788A (en) * | 2021-07-07 | 2021-09-21 | 华亭煤业集团有限责任公司 | Sulfur recovery process by using fuel gas for blending combustion |
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| CN103446859A (en) * | 2013-09-12 | 2013-12-18 | 中国海洋石油总公司 | Treatment method of acid gases in coal-made natural gas |
| CN103446859B (en) * | 2013-09-12 | 2014-10-29 | 中国海洋石油总公司 | Treatment method of acid gases in coal-made natural gas |
| CN106701211A (en) * | 2015-11-12 | 2017-05-24 | 林德股份公司 | Method and device for the selective desulfurization of synthesis gas |
| CN113415788A (en) * | 2021-07-07 | 2021-09-21 | 华亭煤业集团有限责任公司 | Sulfur recovery process by using fuel gas for blending combustion |
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Application publication date: 20130306 |