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 PDF

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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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gas
methanol
column
h2s
claus
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CN2012104119307A
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李红凯
薛天祥
葛雄
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李红凯
薛天祥
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10General improvement of production processes causing greenhouse gases [GHG] emissions
    • Y02P20/12Energy input
    • Y02P20/121Energy efficiency measures, e.g. energy management
    • Y02P20/122Energy efficiency measures, e.g. energy management characterised by the type of apparatus
    • Y02P20/124Boilers, furnaces, lighting or vacuum systems
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10General improvement of production processes causing greenhouse gases [GHG] emissions
    • Y02P20/14Reagents; Educts; Products
    • Y02P20/141Feedstock
    • Y02P20/142Feedstock the feedstock being CO2

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

用于粗煤气或粗煤气的变换气中酸性气体的脱除方法 The method of converting crude gas for the removal of gas or crude gas in the acid gas

技术领域 FIELD

[0001] 本发明涉及一种用于粗煤气或粗煤气的变换气中酸性气体的脱除方法,属于酸性气体脱除方法技术领域。 [0001] The present invention relates to a gas removal process for converting raw gas or raw gas in the acid gas removal process belongs to the technical field of acid gases.

背景技术 Background technique

[0002] 现有的煤化工装置中,其粗煤气(或粗煤气经变换后所得到的变换气,以下简称变换气)所含酸性气体的脱除,采用“低温甲醇洗法”进行净化已被国内、外所公认是最有效、最经济和最节能的方法。 [0002] In a conventional coal chemical plant, which crude gas (or transform the raw gas obtained by gas conversion, hereinafter referred to as shift gas) contained in the acid gas removal, a "Rectisol process" has purifies been recognized by domestic and foreign is the most effective, most economical and most energy-efficient method.

[0003] 在粗煤气被净化的过程中,用低温的甲醇(进入吸收塔的贫甲醇)吸收粗煤气中·的酸性气体,其吸收了酸性气体的叫富甲醇。 [0003] In the crude gas to be purified in the process, a low temperature methanol (methanol lean into the absorber) the acid gas-absorbing crude gas, which is absorbed acid gas is called rich methanol. 富甲醇经热量交換、减压、氮气提和热再生等过程把所吸收的酸性气体放出而变成为贫甲醇。 By heat exchange with methanol-rich, vacuum, nitrogen stripping and regeneration process of the heat absorbed acid gas becomes lean and releasing methanol. 贫甲醇经加压、再与富甲醇进行热量的交换并循环使用,即完成了吸收——解吸——再吸收——再解吸的循环过程。 Pressurized lean methanol, then with methanol-rich heat exchanger and recycled, i.e. complete absorption - desorption - resorption - desorption cycle again.

[0004] 由于煤化工装置是ー个很复杂的装置,即包括很多个子装置构成ー个エ厂,而粗煤气(或变换气)的浄化装置只是复杂的煤化工装置中的ー个子装置。 [0004] Because coal chemical means is ー a very complex apparatus, which includes a lot of sub-apparatus configured ー Ester plants, while the crude gas purifying apparatus (or shift gas) only child apparatus ー complex coal chemical means.

[0005] エ厂中的エ艺子装置或其他如公用工程子装置任ー发生故障均会造成“低温甲醇洗装置”的停车。 [0005] Ester Ester Arts and sub-assembly, or others such as public works sub-assembly plant in either ー failure will cause parking "rectisol device". “低温甲醇洗装置”的停车和再开车,是造成循环甲醇中水含量的増加的原因。 "Rectisol device" stop and then drive, is the cause of the cycle of methanol zo water content added.

[0006] 循环甲醇中水含量的设计值为:彡0. 5% (Wt% ),此时系统无腐蚀。 [0006] The design value of the water circulating in the methanol content: San 0. 5% (Wt%), then the system no corrosion. 当循环甲醇中水含量为:<1.0% (Wt% ),系统会有轻微腐蚀;循环甲醇中水含量为:< 2.0% (Wt% ),系统会有明显腐蚀;循环甲醇中水含量为'く5. 0% (Wt% ),系统会有严重腐蚀。 When the content of the water circulating in methanol: <1.0% (Wt%), the system will be slightly corrosive; methanol circulating water content: <2.0% (Wt%), the system will have significant corrosion; methanol circulating water content ' ku 5. 0% (Wt%), the system will have serious corrosion.

[0007] 为此,为了维持エ厂的长周期运转和节能降耗,必须严格控制循环甲醇中水含量能稳定在设计值,也就是说:一旦循环甲醇中水含量出现超标,必须很快的把它降下来,以杜绝或迅速減少设备与管道的腐蚀发生。 [0007] To this end, in order to maintain long-term operation of the plant Ester and energy saving, must be strictly controlled to stabilize the value of the water content in the design cycle methanol, that is to say: Once the cycle of methanol in water content exceeded the standard, must quickly it down, in order to eliminate or reduce corrosion of equipment and pipelines rapidly occurs. 但是,现有的低温甲醇洗装置对循环甲醇中水含量的控制和稳定缺乏有效的控制手段。 However, the conventional apparatus Rectisol lack of effective means of control and stabilization control loop methanol water content.

发明内容 SUMMARY

[0008] 本发明的目的是为了解决现有的方法对循环甲醇中水含量的控制和稳定缺乏有效的控制手段的问题,进而提供一种用于粗煤气或粗煤气的变换气中酸性气体的脱除方法。 [0008] The object of the present invention is to solve the conventional method lacks effective means of control of the cycle of methanol and stable control of the water content of the problem, thereby providing a method for converting gas or crude gas in the crude gas in the acid gas removal.

[0009] 本发明的目的是通过以下技术方案实现的: [0009] The object of the present invention is achieved by the following technical solution:

[0010] 一种用于粗煤气或粗煤气的变换气中酸性气体的脱除方法,包括:一、用低温的甲醇,吸收粗煤气或变换气中的酸性气体,其吸收了酸性气体的贫甲醇即为富甲醇;ニ、富甲醇经热量交換、减压、进到CO2产品塔,塔顶得到CO2产品,复热后CO2送入尿素装置;三、富甲醇继续减压并到H2S浓缩塔,H2S浓缩塔的上段、H2S+C0S的再吸收段,H2S浓缩塔的下段为氮气提段,自H2S浓缩塔顶引出尾气,复热后排入大气;四、从H2S浓缩塔上段引出的富甲醇是系统中的最低温度,它先与来自热再生塔釜的贫甲醇换冷,再与自吸收塔引出的富甲醇换冷后,导入CO2产品塔的下塔,最終是导入H2S浓缩塔下段的氮气提段•,五、自氮气提段引出的富甲醇经换热后送热再生塔,热再生塔顶逸出的气体经水冷、氨冷后得到含(h2s+cos)+co2+n2的酸性气体,所述酸性气体被送入到克劳斯 Method for removing acidic gas transformation gas [0010] A method for raw gas or raw gas, comprising: a low temperature methanol, shift gas or crude gas absorption of acidic gas, which absorbs the acid gas-depleted methanol is the methanol-rich; ni, rich by heat exchange with methanol under reduced pressure, CO2 into the product column, the overhead product to give CO2, after the CO2 into urea re-heat means; third, methanol-rich continues to H2S and concentrated under reduced pressure column , H2S concentrating tower upper section, reabsorption section H2S + C0S of, H2S concentrating tower lower nitrogen stripping section, since H2S concentrated to the overhead off-gas after the recuperator into the atmosphere; four segments on the column from the H2S concentrated drawn rich methanol is the system the lowest temperature, it first for cooling the lean methanol from the hot regenerated column reactor after methanol-rich and then self absorption tower lead commutation cold, introducing CO2 product column under the tower, ultimately introducing H2S was concentrated under section of the column • nitrogen stripping section, five, nitrogen-enriched methanol from the stripping section drawn through heat exchanger evacuation regeneration tower overhead heat regeneration gas escaping through the water cooling, the resulting ammonia-containing cold (h2s + cos) + co2 + n2 acid gas, the acid gas is fed into the Claus 回收装置;六、热再生塔的大部份抽出液,即贫甲醇,经泵和预冷后到吸收塔继续循环吸收;少部分则被送入甲醇/水分离塔作为进料液;七、原设计的甲醇/水分离塔仅有两股进料,其ー即热再生塔的抽出液;其ニ即进料气分离器的分离液相;八、把来自热再生塔顶分离器的纯甲醇用泵压送一部分到热再生塔,另一部分到甲醇/水分离塔,并分别作为热再生塔和甲醇/水分离塔的塔顶回流液;九、热再生塔顶的排出气体被送到克劳斯硫回收装置作原料气,把原料气配入化学当量的空气经加热后进到ニ级或三级克劳斯催化剂床层,在克劳斯催化剂床层上发生克劳斯反应;十、反应后的气体经冷却、冷凝而进入分离器中被分离成气、液两相,液相为:液体硫黄;气相为:含H2S、C0S和游离氧的氧化性气体,该氧化性气体经加热到Co-Mo加氢催化剂(或水解催化 Recovery; six, most of the hot regenerated column was withdrawn, i.e. lean methanol, dried and pre-cooling the pump continues to loop back to the absorber tower; were fed to a small portion of methanol / water separation column as a feed solution; VII. original design methanol / water separation column just two feed which ー aspirate i.e. thermal regeneration column; ni i.e. which feed gas separator separating liquid; eight, the regeneration heat from the overhead separator pure feeding a portion of the methanol pumped to the heat regeneration tower, another portion of the methanol / water separation column, and the overhead as each heat regeneration tower reflux and methanol / water separation column; nine, thermal regeneration of the exhaust gas is supplied to the overhead Claus sulfur recovery unit as a raw material gas, the raw material gas with the stoichiometric air heated to a backward stage Ni or three Claus catalyst bed, the Claus reaction takes place on Claus catalyst bed; ten , the reaction was cooled gas, condensed into the separator is separated into gas and liquid phases, the liquid phase: liquid sulfur; gas as: containing H2S, C0S free oxygen and oxidizing gas, the oxidizing gas through the heating the Co-Mo hydrogenation catalyst (or catalytic hydrolysis 剂)的活性温度,并被送到装有Co-Mo加氢催化剂(或水解催化剂)的反应器中;十一、在所述反应器中,氧化性气体被还原,即S02、C0S被还原成H2S、游离氧则被加氢成水;所述还原性气体再经初冷、脱水干燥和终冷后,送到低温甲醇洗装置的H2S浓缩塔下塔的氮气提段;在H2S浓缩塔的下塔被来自从上塔流下的循环甲醇所吸收,吸收了酸性气体的循环甲醇则自塔底引出,经复热后被压送到热再生塔;十二、热再生塔顶排出的混合酸性气体再经冷却、冷凝和分离后又被送到克劳斯硫回收装置,在克劳斯硫回收装置中,混合酸性气体经ニ级或三级克劳斯催化剂床层反应后,经冷却和两相分离,液相为:液体硫黄,气相为:含有SO2的氧化性气体;十三、把氧化性气体加热,加热温度为200±5°C,压カ为0. 04Mpa并送到装有Co-Mo加氢催化剂的反应器(或水解催化剂) Agent) activation temperature, and it is sent to a hydrogenation catalyst containing Co-Mo (or hydrolysis catalyst) reactor; XI, in the reactor, the oxidizing gas is reduced, i.e. S02, C0S is reduced into H2S, were free oxygen is hydrogenated to water; the reducing gas and then the cold First, after the final cooling and dried, to Rectisol apparatus H2S column was concentrated under a nitrogen stripping section of the column; H2S in the concentrating tower the tower was absorbed from the circulating flow from the column with methanol, the methanol loop absorbed acid gas is drawn from the bottom, after being pressure-fed by the re-heat the thermal regeneration tower; XII thermal regeneration acidic mixture discharged overhead gas is then cooled, condensed and after separation is supplied to the Claus sulfur recovery unit, in the Claus sulfur recovery unit, the acid gas mixture through the catalyst bed of the Claus reaction after three stages or Ni, and cooled two phases were separated, the liquid phase: liquid sulfur, the gas phase is: an oxidizing gas containing SO2; and thirteen, the oxidizing gas is heated, the heating temperature was 200 ± 5 ° C, ka is 0. 04Mpa pressure and sent with Co-Mo catalyst of the hydrogenation reactor (or hydrolysis catalyst) ,并把氧化性气体中的SO2XOS被还原成H2S,游离氧还原成水,最后为h2s+h2o+惰性气的混合气;十四、H2S+H20+情性气的混合气,再经0±5°C初冷、脱水干燥、0. 45Mpa加压和终冷后,终冷温度为_33±5°C,压カ为0. 40Mpa,重又返回到低温甲醇洗装置H2S浓缩塔的下塔,并被自塔上部流下的循环甲醇吸收,自塔底引出的循环甲醇经加热被送到热再生塔,如此实现循环操作。 And the oxidizing gas SO2XOS is reduced to H2S, free oxygen is reduced to water and finally mixed gas h2s + h2o + inert gas; fourteen, H2S + H20 + mixed gas affective gas, and then the 0 ± 5 ° First C cold, dehydration, 0. 45Mpa and the rear end of the cold pressing, final cooling temperature of _33 ± 5 ° C, pressure ka is 0. 40Mpa, again returned to the Rectisol means H2S concentration under the column of the column, the upper portion of the column and a stream from the methanol absorption cycle, the methanol from the bottom cycle heat extraction is sent to the regeneration tower is heated, so to achieve the cycle operation.

[0011] 本发明具有以下优点:本发明的方法由于严格控制住了循环甲醇中的水含量,因此使设备的使用寿命延长。 [0011] The present invention has the following advantages: The method of the present invention due to the strict control the water content in the methanol loop, so that the extended life of the equipment. 另外腐蚀的減少使得流程中的换热器的换热热阻降低,传热温差減少,使冷冻量节省,达到了节能降耗的目的。 Further reduction in the corrosion resistance such that the flow of the heat exchanger is reduced, reducing the heat transfer temperature difference, the amount of the refrigeration savings achieve energy saving purposes.

[0012] 另外,本发明不仅大大地简化了克劳斯硫回收装置中尾气处理系统的流程,还可以使酸性尾气达到“零排放”,是两全齐美的好办法。 [0012] Further, the present invention not only greatly simplifies the Claus sulfur recovery unit in the exhaust gas flow treatment system, it is also possible to achieve the acid off-gas "zero emissions", is a good way of both worlds.

具体实施方式 Detailed ways

[0013] 下面将对本发明做进ー步的详细说明:本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式,但本发明的保护范围不限于下述实施例。 [0013] The following detailed description will be made into the present invention ー steps: In the present embodiments of the present invention is a technical premise, detailed embodiments given, but the scope of the present invention is not limited to the following examples .

[0014] 本实施例所涉及的一种用于粗煤气或粗煤气的变换气中酸性气体的脱除方法,包括:一、用低温的甲醇,(即入吸收塔顶的贫甲醇)吸收粗煤气或变换气中的酸性气体,其吸收了酸性气体的贫甲醇即为富甲醇;ニ、富甲醇经热量交換、减压、进到CO2产品塔,塔顶得到CO2产品,复热后CO2送入尿素装置;三、富甲醇继续减压并到H2S浓缩塔,H2S浓缩塔的上段、H2S+C0S的再吸收段,H2S浓缩塔的下段为氮气提段,自H2S浓缩塔顶引出尾气,复热后排入大气;四、从H2S浓缩塔上段引出的富甲醇是系统中的最低温度,它先与来自热再生塔釜的贫甲醇换冷,再与自吸收塔弓I出的富甲醇换冷后,导入CO2产品塔的下塔,最終是导入H2S浓缩塔下段的氮气提段;五、自氮气提段引出的富甲醇经换热后送热再生塔,热再生塔顶逸出的气体经水冷、氨冷后得到含(h2s+cos)+co2+n2 [0014] The gas removal process for converting crude gas or crude gas according to a present embodiment of the acid gases, comprising: a low temperature methanol, (i.e., absorption of methanol into the overhead lean) absorbent crude gas shift gas or acid gas, which absorbs the acid gas-lean methanol is the methanol-rich; Ni-rich methanol-exchanged by the heat, pressure, CO2 product into the column, the overhead product to give CO2, after the CO2 sent to re-heat urea means; third, methanol-rich continued under reduced pressure and the H2S concentration column, H2S concentrating tower upper section, the reabsorption section H2S + C0S of, H2S concentration column nitrogen stripping section under segment, since H2S concentrated to the overhead off-gas complex after the heat into the atmosphere; Fourth, concentrated H2S from the rich methanol extraction tower section is the lowest temperature in the system, it first for cold and hot regenerated lean methanol from the column bottom, and then from the absorption column and the bow of the methanol-rich change I after cooling, the product introduced into the tower at the tower CO2, H2S and concentrated ultimately introducing nitrogen stripping section lower section of the tower; five, nitrogen-enriched methanol from the stripping section drawn through a heat exchanger evacuation thermal regeneration tower that escaping gas heat regeneration was cooled, the obtained ammonia containing cold (h2s + cos) + co2 + n2 酸性气体,所述酸性气体被送入到克劳斯硫回收装置;六、热再生塔的大部份抽出液,即贫甲醇,经泵和预冷后到吸收塔继续循环吸收;少部分被送入甲醇/水分离塔作为进料液;七、原低温甲醇洗装置中的甲醇/水分离塔有两股进料,其ー即热再生塔的抽出液;其ニ即进料气分离器的分离液相;八、把来自热再生塔顶分离器的纯甲醇(即100%甲醇)、用泵压送一部分到热再生塔,另一部分到甲醇/水分离塔,并分别作为作为热再生塔和甲醇/水分离塔的塔顶回流液;九、热再生塔顶的排出气体被送到克劳斯硫回收装置作原料气,把原料气配入化学当量的空气经加热后进到ニ级或三级克劳斯催化剂床层,在克劳斯催化剂床层上发生克劳斯反应;十、反应后的气体经冷却、冷凝而进入分离器中被分离成气、液两相,液相为:液体硫黄;气相为:氧化性(含S0 Acid gas, the acid gas is fed into the Claus sulfur recovery unit; six, most of the hot regenerated column was withdrawn, i.e. lean methanol, dried and pre-cooling the pump continues to loop back to the absorber tower; a small portion is into methanol / water separation column as a feed solution; seven original low methoxide methanol / water separation column washing device has two feed which ー i.e. hot regenerated column was withdrawn; ni i.e. which feed gas separator the phases were separated; eight, the regeneration heat from the overhead separator pure methanol (i.e., 100% methanol), to a portion of the pump pressure-feeding hot regeneration tower, another portion of the methanol / water separation column, and were used as a thermal regeneration column and methanol / water separation column overhead reflux; IX, the exhaust gas heat regeneration overhead Claus sulfur recovery unit is supplied as a raw material gas, the raw material gas with the stoichiometric air heated to a backward stage ni or three Claus catalyst bed, the Claus reaction takes place on Claus catalyst bed; X. gas after reaction was cooled and condensed into the separator is separated into gas and liquid phases, the liquid phase It is: liquid sulfur; gas is: oxidative (including S0 2、C0S和游离氧等)气体,该氧化性气体经加热到Co-Mo加氢催化剂(或水解催化剂)的活性温度,并被送到装有Co-Mo加氢催化剂(或水解催化剂)的反应器中;十一、在所述反应器中,氧化性气体被还原,即S02、COS还原成H2S、游离氧则被加氢成水;所述还原性气体再经初冷、脱水干燥和终冷后,送到低温甲醇洗装置的H2S浓缩塔下塔的氮气提段;在H2S浓缩塔的下塔被来自从上塔流下的循环甲醇所吸收,吸收了酸性气体的循环甲醇则自塔底引出,经复热后被压送到热再生塔;十二、热再生塔顶排出的混合酸性气体(包括新进到低温甲醇洗装置的进料气中的酸性气和克劳斯硫回收装置中、未转化的H2S(< 10%)等气体两部分)再经冷却、分离和复热后又被送到克劳斯硫回收装置,在克劳斯硫回收装置中,混合酸性气体经ニ级或三级克劳斯催化剂床层反应后,经冷 2, C0S and free oxygen) gas, the oxidizing gas is heated to a Co-Mo hydrotreating catalyst (catalyst or hydrolysis) of the active temperature and sent to a hydrogenation catalyst containing Co-Mo (or hydrolysis catalyst) reactor; XI, in the reactor, the oxidizing gas is reduced, i.e. S02, COS reduced to H2S, were free oxygen is hydrogenated to water; the reducing gas and then cooled by the early, and dried after final cooling, to the Rectisol apparatus H2S column was concentrated under a nitrogen stripping section of the column; are absorbed from flowing down the column from the circulating H2S methanol and concentrated under column tower, absorption of the acid gas from the bottom of the cycle of methanol lead, after being pressure-fed by the re-heat the thermal regeneration tower; XII overhead hot gas discharged from the mixed acid regeneration (including new devices into the Rectisol feed gas in the acid gas and Claus sulfur recovery , the unconverted H2S (<10%) and other gases in two parts) and then cooling, separating and then re-heat is supplied to the Claus sulfur recovery unit, in the Claus sulfur recovery unit, the acid gas by mixing Ni after the reaction stage or three Claus catalyst bed, the cold 和两相分离,液相为:液体硫黄,气相为:含有S02、COS和游离氧的氧化性气体(温度:约170 0C ;压力:0. 04Mpa(G));十三、把氧化性气体加热,加热温度为200±5°C (取决于Co-Mo加氢催化剂或水解催化剂的活性温度);压カ为0. 04Mpa(G))并送到装有Co-Mo加氢催化剂或水解催化剂的反应器中,并把氧化性气体中的S02、COS还原成H2S、游离氧还原成水,最终为含有H2S+H20+惰性气的混合气;十四、H2S+H20+惰性气的混合气再经0±5°C初冷、脱水干燥、0. 45Mpa加压和终冷后,终冷温度为_33±5°C,压カ为0. 40Mpa,重又送到低温甲醇洗装置H2S浓缩塔的下塔(即氮气提段),并被自塔上部流下的循环甲醇吸收,自塔底引出的循环甲醇经加热被送到热再生塔,如此实现循环操作。 And two phases were separated, the liquid phase: liquid sulfur, the gas phase is: an oxidizing gas containing S02, COS, and free oxygen (temperature: about 170 0C; Pressure:. 0 04Mpa (G)); XIII, the oxidizing gas heating, the heating temperature was 200 ± 5 ° C (depending on the temperature of the active hydrogenation catalyst or Co-Mo catalyst of hydrolysis); ka pressure of 0. 04Mpa (G)) and fed with hydrogenation catalyst or Co-Mo hydrolysis reactor catalyst and the oxidizing gas in S02, COS reduced to H2S, free oxygen is reduced to water, eventually mixed gas containing H2S + H20 + inert gas; fourteen, H2S + H20 + inert gas mixture gas again by 0 ± 5 ° C cold First, dried, 0. 45Mpa and the rear end of the cold pressing, final cooling temperature of _33 ± 5 ° C, pressure ka is 0. 40Mpa, to again concentrate the Rectisol means H2S column in the column (i.e., a nitrogen stripping section), the upper portion of the column and a stream from the methanol absorption cycle, the methanol from the bottom cycle heat extraction is sent to the regeneration tower is heated, so to achieve the cycle operation.

[0015] 所述甲醇/水分离塔的塔顶温度为85〜95°C,塔顶回流液的入塔温度为35〜450C,来自热再生塔塔釜液的温度为65〜75°C,来自进料气分离器的甲醇/水液相温度为46〜55°C,甲醇/水分离塔的塔釜温度为126〜136°C ;所述甲醇/水分离塔的塔顶操作压カ为0. 24〜0. 3Mpa,塔釜操作压カ为0. 25〜0. 3IMpa0 [0015] The methanol / water separation column top temperature of 85~95 ° C, the temperature of the column as overhead reflux liquid 35~450C, the temperature of column bottom liquid from the thermal regeneration of 65~75 ° C, the methanol gas from the feed separator / water liquidus temperature of 46~55 ° C, the temperature of the column reactor the methanol / water separation column is 126~136 ° C; overhead of the operating pressure grades methanol / water separation column is 0. 24~0. 3Mpa, the operating pressure of column reactor grades of 0. 25~0. 3IMpa0

[0016] 本发明用无水甲醇作甲醇/水分离塔的塔顶回流液时,随着塔顶回流量的増加,就可能大大降低甲醇/水分离塔塔顶逸出气体的含水量、甚致于可以无水。 When [0016] the present invention with anhydrous methanol as methanol / water separation column overhead reflux, with the return flow to increase in overhead, it is possible to significantly reduce the water content of methanol / water separation column overhead gas escaping, even It can be induced to dry. 即不会再出现水分在甲醇/水分离塔和热再生塔之间的循环,从而会很快地使循环甲醇中的水含量降到设计值。 I.e., water will no longer appear in methanol / water separation column and the heat cycle between regeneration tower, which will rapidly circulating the water content of methanol drops to the design value.

[0017] 本发明把未转化的H2S(彡10% )等气体再送回到“低温甲醇洗装置”的H2S浓缩塔中重新被循环甲醇吸收。 [0017] The present invention unconverted H2S (San 10%) H2S gas such as sending back to the concentrating tower "Rectisol means" re-absorbed methanol is circulated. 从而,在“克劳斯硫回收装置”中不需再新建既复杂、投资又高的尾气处理系统,既简化了操作、降低了エ厂的投资,又达到含H2S尾气的“零排放”减少对环境大气的污染。 Thus, "Claus sulfur recovery unit" in the complicated do not need to create a new, high investment and exhaust gas treatment system, not only simplifies operation, reduces Ester plant investment, and H2S-containing off-gas to achieve "zero discharge" reduced environmental pollution of the atmosphere.

[0018] 以上所述,仅为本发明较佳的具体实施方式,这些具体实施方式都是基于本发明整体构思下的不同实现方式,而且本发明的保护范围并不局限于此,任何熟悉本技术领域 [0018] The above are only preferred specific embodiment of the present invention embodiments, these embodiments are based on different implementations of the overall concept of the present invention, and the scope of the present invention is not limited thereto, any skilled fIELD

的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。 In the art within the technical scope of the present invention is disclosed, variations or replacement that can be easily thought, shall fall within the protection scope of the present invention. 因此,本发明的保护范围应该以权利要求书的保护范围为准。 Accordingly, the scope of the present invention, the scope of the claims should prevail.

Claims (2)

1. 一种用于粗煤气或粗煤气的变换气中酸性气体的脱除方法,其特征在于,一、用低温的甲醇,吸收粗煤气或变换气中的酸性气体,其吸收了酸性气体的贫甲醇即为富甲醇;二、富甲醇经热量交换、减压、进到CO2产品塔,塔顶得到CO2产品,复热后CO2送入尿素装置;三、富甲醇继续减压并到H2S浓缩塔,H2S浓缩塔的上段为H2S+C0S的再吸收段,H2S浓缩塔的下段为氮气提段,自H2S浓缩塔顶引出尾气,复热后排入大气;四、从H2S浓缩塔上段引出的富甲醇是系统中的最低温度,它先与来自热再生塔釜的贫甲醇换冷,再与自吸收塔引出的富甲醇换冷后,导入CO2产品塔的下塔,最终导入H2S浓缩塔下段的氮气提段;五、自氮气提段引出的富甲醇经换热后送热再生塔,热再生塔顶逸出的气体经水冷、氨冷后得到含(H2S+C0S)+C02+N2的酸性气体,并被送入到克劳斯硫回收装置; 1. A method for converting gas removal process the crude gas in the crude gas or acid gases, wherein a, low temperature methanol, shift gas or crude gas absorption of acidic gas, which absorbs the acid gases methanol is the rich-lean methanol; second, by heat exchange of the laden methanol under reduced pressure, CO2 into the product column, the overhead product to give CO2, after the CO2 into urea re-heat means; third, methanol-rich continues to H2S and concentrated under reduced pressure column, H2S concentrating tower upper section to the reabsorption section H2S + C0S of, H2S concentrating tower lower nitrogen stripping section, since H2S concentrated to the overhead off-gas after the recuperator into the atmosphere; Fourth, the upper lead concentrate from H2S column methanol-rich the system the lowest temperature, it first for cooling the lean methanol from the hot regenerated column reactor after methanol-rich and then self absorption tower lead commutation cold, introducing CO2 product column under the tower, finally introduced H2S was concentrated under section of the column nitrogen stripping section; 5, methanol-rich regeneration tower heat exchanging heat evacuation from the nitrogen stripping section drawn, the thermal regeneration overhead gas escaping through the water cooling, the obtained ammonia containing cold (H2S + C0S) + C02 + N2 of acid gas, and fed to a Claus sulfur recovery unit; 六、热再生塔的抽出液,即贫甲醇,绝大部分经泵压送和予冷后到吸收塔继续循环吸收;少部分则被送入甲醇/水分离塔作为进料液;七、甲醇/水分离塔有两股进料,其一即热再生塔的抽出液;其二即进料气分离器的分离液相;八、把来自热再生塔顶分离器并用泵压送的纯甲醇除一部分仍送到热再生塔外,另一部分则送到甲醇/水分离塔,并作为塔顶回流液;九、热再生塔顶的排出气体经冷却、冷凝和分离后,被送到克劳斯硫回收装置作原料气,把原料气配入化学当量的空气经加热后进到二级或三级克劳斯催化剂床层,在克劳斯催化剂床层上发生克劳斯反应;十、反应后的气体经冷却、冷凝而进入分离器中被分离成气、液两相,液相为:液体硫黄;气相为:含有化学硫的氧化性气体,该氧化性气体经加热到Co-Mo加氢催化剂的活性温度后,再送到装有Co Six, aspirate thermal regeneration column, i.e. after the lean methanol, most of the feeding through the pump and pressure continues to cycle the absorbent to the absorption column cold; were fed to a small portion of methanol / water separation column as a feed solution; seven, methanol / water separation column has two feed, i.e. one of the regeneration heat withdrawn liquid column; second liquid phase that is separated into the feed gas separator; eight, the regeneration heat from the overhead separator and the pump pressure-feeding with pure methanol addition still part of the regeneration tower to the heat, the other part is sent to the methanol / water separation column, and the column top as reflux; IX overhead thermal regeneration of the exhaust gas after cooling, condensation and separation, is supplied to Claus sulfur recovery air as the raw material gas, the raw material gas with the heated chemical equivalents of a secondary or tertiary backward to Claus catalyst bed, the Claus reaction takes place on Claus catalyst bed; ten, after the reaction the gas is cooled and condensed into the separator is separated into gas and liquid phases, the liquid phase: liquid sulfur; gas as: an oxidizing gas containing sulfur chemistry, the oxidizing gas is heated to a Co-Mo hydrogenating after the catalyst activation temperature, and then sent with Co -Mo加氢催化剂的反应器中;十一、在所述反应器中,氧化性气体被还原,即SO2还原成H2S、COS还原成H2S、游离氧则被加氢成水;所述还原性气体再经初冷、脱水干燥和终冷后,又被送到低温甲醇洗装置的H2S浓缩塔下塔的氮气提段;所述还原性气体在H2S浓缩塔的下塔被来自从上塔流下的循环甲醇所吸收,循环甲醇则从塔底引出,复热后被压送到热再生塔;十二、热再生塔顶排出的混合酸性气体经冷却、冷凝和分离后又被送到克劳斯硫回收装置。 The reactor -Mo hydrogenation catalyst; XI, in the reactor, the oxidizing gas is reduced, i.e. reduction of SO2 to H2S, COS reduced to H2S, were free oxygen is hydrogenated to water; the reducing First gas and then by cooling, dehydration, and after final cooling, it was sent to the Rectisol apparatus H2S column was concentrated under a nitrogen stripping section of the column; the reducing gas is from the stream from the column in the lower column H2S concentrating tower cyclic absorbed methanol, methanol from the bottom circulation leads, after pressed to re-heat the thermal regeneration tower; XII overhead hot gas discharged from the mixed acid regeneration cooled, condensed and after separation is supplied to the Claus sulfur recovery unit. 在克劳斯硫回收装置中,混合酸性气体经二级或三级克劳斯催化剂床层反应后,经冷却和两相分离,液相为:液体硫黄,气相为:含有S02、COS和游离氧的氧化性气体;十三、把氧化性气体加热,加热温度约为:200±5°C,压力为:0. 04Mpa并送到装有Co-Mo加氢催化剂或水解催化剂的反应器中,并把氧化性气体中的S02、COS和游离氧还原成H2S+H20+惰性气;十四、H2S+H20+惰性气再经0±5°C初冷、脱水干燥、O. 45Mpa加压和终冷后,终冷温度为_33±5°C,压力为O. 40Mpa,重又送到低温甲醇洗装置H2S浓缩塔的下塔,并被自塔上部流下的循环甲醇吸收,自塔底引出的循环甲醇经加热被送到热再生塔,如此实现循环操作。 In the Claus sulfur recovery unit, the acid gas mixture, after two or three Claus catalyst bed reactor, cooled, and two phases were separated, the liquid phase: liquid sulfur, the gas phase is: comprising S02, COS, and the free oxygen-oxidizing gas; XIII, the oxidizing gas is heated, the heating temperature is about: 200 ± 5 ° C, pressure: 0 04Mpa and fed to a reactor equipped with a hydrogenation catalyst or Co-Mo catalyst in the hydrolysis. and the oxidizing gas in S02, COS, and free oxygen is reduced to H2S + H20 + inert gas; fourteen, H2S + H20 + inert gas and then by 0 ± 5 ° C First cooling, dried, O 45Mpa pressing and final. after cooling, final cooling temperature of _33 ± 5 ° C, a pressure of O. 40Mpa, again concentrated to a low temperature methanol apparatus H2S wash column under the tower, the tower and flows down from the upper methanol absorption cycle, leads from the bottom circulating the heated methanol is fed to thermal regeneration column, so to achieve the cycle operation.
2.根据权利要求I所述的用于粗煤气或粗煤气的变换气中酸性气体的脱除方法,其特征在于,所述甲醇/水分离塔的塔顶温度为85〜95°C,新增塔顶回流液的入塔温度为35〜450C,来自热再生塔塔釜液的温度为65〜75°C,来自进料气分离器的甲醇/水液相温度为46〜55°C,甲醇/水分离塔的塔釜温度为126〜136°C ;甲醇/水分离塔的塔顶操作压力为O. 24〜O. 3Mpa,塔釜操作压力为O. 25〜O. 3IMpa0 2. I raw gas removal process for converting a gas or crude gas in the acid gas according to claim, wherein said methanol / water separation column top temperature of 85~95 ° C, a new by overhead reflux liquid into the column temperature 35~450C, the temperature of column bottom liquid from the thermal regeneration of 65~75 ° C, the methanol gas from the feed separator / water liquidus temperature of 46~55 ° C, methanol / water separation column bottoms temperature of 126~136 ° C; methanol / water separation column overhead operating pressure O. 24~O 3Mpa, the operating pressure of the column reactor O. 25~O 3IMpa0..
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Cited By (1)

* Cited by examiner, † Cited by third party
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

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4242108A (en) * 1979-11-07 1980-12-30 Air Products And Chemicals, Inc. Hydrogen sulfide concentrator for acid gas removal systems
US4430316A (en) * 1980-12-18 1984-02-07 Linde Aktiengesellschaft Scrubbing system yielding high concentration of hydrogen sulfide
US4475347A (en) * 1982-09-16 1984-10-09 Air Products And Chemicals, Inc. Process for separating carbon dioxide and sulfur-containing gases from a synthetic fuel production process off-gas
CN1872392A (en) * 2005-06-02 2006-12-06 中国寰球工程公司 Method for purifying carbonyl gas through methanol in low temperature
CN101418246A (en) * 2008-12-05 2009-04-29 华陆工程科技有限责任公司 Low temperature methanol washing integrated Claus sulfur recovery system and process
CN201439518U (en) * 2009-06-12 2010-04-21 北京新峰泰克工程技术有限公司 System for purifying crude synthetic gas with low-temperature methanol
CN101874967A (en) * 2009-12-18 2010-11-03 中国五环工程有限公司 Process for removing acid gas with low-temperature methanol solution
CN102489119A (en) * 2011-11-25 2012-06-13 中国神华煤制油化工有限公司 Low-temperature methanol washing and CO2 capture combined method
CN102631827A (en) * 2012-04-11 2012-08-15 山东三维石化工程股份有限公司 Zero-emission sulfur recovery technology combined with low-temperature methanol washing acid gas treatment

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4242108A (en) * 1979-11-07 1980-12-30 Air Products And Chemicals, Inc. Hydrogen sulfide concentrator for acid gas removal systems
US4430316A (en) * 1980-12-18 1984-02-07 Linde Aktiengesellschaft Scrubbing system yielding high concentration of hydrogen sulfide
US4475347A (en) * 1982-09-16 1984-10-09 Air Products And Chemicals, Inc. Process for separating carbon dioxide and sulfur-containing gases from a synthetic fuel production process off-gas
CN1872392A (en) * 2005-06-02 2006-12-06 中国寰球工程公司 Method for purifying carbonyl gas through methanol in low temperature
CN101418246A (en) * 2008-12-05 2009-04-29 华陆工程科技有限责任公司 Low temperature methanol washing integrated Claus sulfur recovery system and process
CN201439518U (en) * 2009-06-12 2010-04-21 北京新峰泰克工程技术有限公司 System for purifying crude synthetic gas with low-temperature methanol
CN101874967A (en) * 2009-12-18 2010-11-03 中国五环工程有限公司 Process for removing acid gas with low-temperature methanol solution
CN102489119A (en) * 2011-11-25 2012-06-13 中国神华煤制油化工有限公司 Low-temperature methanol washing and CO2 capture combined method
CN102631827A (en) * 2012-04-11 2012-08-15 山东三维石化工程股份有限公司 Zero-emission sulfur recovery technology combined with low-temperature methanol washing acid gas treatment

Cited By (2)

* Cited by examiner, † Cited by third party
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
CN103446859B (en) 2013-09-12 2014-10-29 中国海洋石油总公司 A method for acid gas treatment SNG

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