CN1040744A - 从流体流中除去硫化氢 - Google Patents
从流体流中除去硫化氢 Download PDFInfo
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- CN1040744A CN1040744A CN89107762A CN89107762A CN1040744A CN 1040744 A CN1040744 A CN 1040744A CN 89107762 A CN89107762 A CN 89107762A CN 89107762 A CN89107762 A CN 89107762A CN 1040744 A CN1040744 A CN 1040744A
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- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 13
- 239000012530 fluid Substances 0.000 title claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000013522 chelant Substances 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
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- 229930006000 Sucrose Natural products 0.000 description 1
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- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/05—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by wet processes
-
- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
- F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
- F03G4/00—Devices for producing mechanical power from geothermal energy
- F03G4/074—Safety arrangements
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- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Treating Waste Gases (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Gas Separation By Absorption (AREA)
- Removal Of Specific Substances (AREA)
Abstract
用含有正铁螯合物和含有磺基，羧基或它们的混合物的水溶液作为一种阻催化剂可以达到基本上完全除去在酸气流或地热流中的硫化氢。在这过程中正铁螯合物还原为亚铁螯合物，并通过含有气流的氧气再生为正铁螯合物。本发明的聚合催化剂在铁的0.005至0.4浓度下抑制了氧化及螯合剂的损耗。
Description
本发明涉及一种从流体流中除去硫化氢（H2S）的方法，该流体用正铁螯合物的水溶液进行处理，基本上全部除去其中所含的硫化氢气体。
在现有技术中，用铁螯合物从酸气流中除去H2S是公知的，例如，美国专利4，622，212中第一纵栏及第二纵栏提出了可添加各种有机化合物用作铁螯合物的稳定剂，在下列的美国专利中也有说明：US4，382，918;4，388，293;4，400，368;4，421，733和4，461，754。
过去使用的棕色抑制剂通常在大量存在时才有效，并且已知通过降解过程消耗抑制剂，这就增加了抑制剂的复杂性，对H2S螯合物回收处理中也要损耗，因此，长时期以来一直寻找不需要大量存在也不需经常补充的抑制剂。
本发明是一种利用铁螯合物溶液除去酸气流中H2S的方法，在酸气流中铁螯合物溶液与酸气接触，通过加入一定量的阴离子聚合物从降解作用中受到抑制。本发明的进一步的目的是提供一种含铁螯合物和阴离子聚合物的水溶液的组合物。
本发明的方法有如下步骤：
A）在接触区内，酸气或地热流与含有下列成分的水溶液相接触，
（1）有效量的铁（Ⅲ）螯合物，和
（2）一定量的含有磺基，羧基或他们的混合物的水溶阴离子聚合物，该水溶液对稳定所述的螯合物是有效的。
在所述的溶液中铁螯合物还原为铁（Ⅱ）螯合物，产生净化气流和硫化颗粒。
B）在氧化区内再生所述的还原铁螯合物为铁（Ⅲ）螯合物。
C）至少除去一部份所述的硫化颗粒。和
D）再循环所述的再生铁螯合物至所述的接触区。
在已知的有机化合物的使用范围内，本发明的有利之处是不使用有机化合物重量的1.0%至5.0%，而可使用很小量的阴离子聚合物，即在百万分之一的范围内。
本发明制备正铁螯合物中所用的螯合剂包括那些形成可溶于水的螯合物的螯合剂或配位剂。这些螯合剂的代表是氨基羧酸，例如，次氮基三乙酸，N-羟乙基亚氨基二乙酸，乙二胺四乙酸、N-羟乙基乙二胺三乙酸，二亚乙基三胺五乙酸，环己二胺四乙酸，三亚乙基四胺六乙酸等，包括它们的盐。
有用的螯合剂的另一实例是氨基膦酸，例如：乙二胺四亚甲基膦酸，氨基三亚甲基膦酸，二亚乙基三胺五亚甲基膦酸;膦酸，例如，1-羟基亚乙基-1，1-二膦酸，2-膦酰基乙酸，2-膦酰基丙酸和2-膦酰基乙烷1，2-二羧酸;多羟基螯合剂，例如，单糖和糖类（例如二糖，如蔗糖，乳糖和麦芽糖），糖酸（如葡糖酸或葡糖庚酸）;其它多元醇，例如，山梨醇和甘露糖醇等。
其它有用的螯合剂是磺化油和三乙醇胺。
在制备正铁螯合物时，上述各种螯合剂中以使用乙二胺四乙酸，N-羟乙基乙二胺三乙酸，次氮基三乙酸最为有利。
在循环溶液中被螯合的铁的浓度应该是铁的百万分之（ppm）100至50000的范围内，最好是在1000至10000ppm的范围内。
螯合物溶液的循环速率决定于环流中硫化氢的含量，一般来说，循环速率对进入反应区的每摩尔H2S来说为1至6摩尔，最好是2至4摩尔的正铁螯合物是足够的，如此以一较高的正铁螯合物浓度则可用于较低的循环速率。
本发明有用的水溶聚合物的例子包括有磺基，羧基或它们的混合物的阴离子聚合物，本发明所使用的这样的聚合物是聚苯乙烯磺酸钠盐，苯乙烯磺化钠和丙烯酰胺的共聚物和聚乙烯磺酸的均聚物以及与丙烯酰胺的共聚物。
优选的水可溶阴离子聚合物团是甲基丙烯酰胺/异丁烯酸聚合物。其它的例子是（1）聚丙烯酸或聚异丁烯酸或他们的盐，（2）部份水解了的聚丙烯酰胺或聚甲基丙烯酰胺，（3）丙烯酸或异丁烯酸或它们的盐和丙烯酰胺或甲基丙烯酰胺的共聚物，（4）乙烯基磺酸或它的盐和丙烯酰胺或甲基丙烯酰胺的共聚物，（5）2-丙烯酰基酰氨基-2-甲基-丙烷磺酸盐和丙烯酸或异丁烯酸盐及丙烯酰胺或甲基丙烯酰胺的三元共聚物。这些阴离子共聚物是已知的，可以从市场上得到，可参阅比利时专利628018;美国专利2，909，508;3，617，572;4，479，879。
前述的阴离子聚合物的作用是作为螯合物降解的抑制剂，在循环溶液中采用的量为铁的0.005至0.04。上述范围可认为是催化剂的有效量，一般来说，若在使用时小于上述范围的量则达不到所希的效果。使用抑制剂的量可直至它的溶性极限。但大于上述可取范围是不经济的，较好的范围是铁的0.005至0.1，最好的范围是铁的0.1至0.4。
气流与水溶液接触时间至少为0.05秒，更可取的是在0.2至1.0秒范围内。
正铁螯合物水溶液的pH值是6至11，更可取的是7.0至9.0，PH值在6以下对H2S的除去是不适宜的。pH值在11以上则溶液就不能保持正铁螯合物为可溶的形态。
一般来说，要提供具有一定容量的曝气池或槽，螯合剂溶液在那里滞留时间为0.1至5小时，更好为0.5至2小时，在氧化区内，空气或包含气体的氧气以一定的速率向氧化区内喷射，至少达到被处理的每摩尔的H2S中有0.5摩尔的氧气。一般来说，比率为每摩尔H2S 0.6至20.0摩尔的氧，更好为每摩尔H2S 1.0至10.0摩尔的氧。
在流动系统任一便利处提供了除去固体硫的方法。任何一种合适的方法都可以使用，包括但不限于过滤，沉淀或溶化，通过此系统在溶液的每一个通道可以完全除去硫，或用另一方法仅除去硫的一部份，因而容许固体硫在溶液中聚集到容许的限额。
下面用实例和操作进一步说明本发明。
操作1
在一个2升的槽内加入下列组分：71.5克Na2B4O7.10H2O，65.3克K2HPO4，1350毫升H2O和150毫升5%Fe（NO3）3溶液与羟基乙基乙二胺三乙酸（HEDTA）的螯合物。上述组分溶解后，空气和5%的H2S（剩余氮气）的混合物分别以44SCFH（每小时标准立方呎）或1.2米3/小时和0.5SCFH（0.01米3/小时）的速率喷入同时搅拌着的溶液内。大约12小时后，气体停止流动，在运转过程中取样对HEDTA配位体进行分析。
实例1至5
重复操作，但在水溶液中含有本发明的聚合物抑制剂，各种量的具有百分之4.8摩尔丙烯酸的低电荷密度聚丙烯酰胺-丙烯酸共聚物的钠盐，在市场上可作为烃乳化剂得到（来自EXXOn化学制品Jay flocTM803），其结果由表1示出。
表1
添加剂 每份Fe的 Na3HEDTA
添加剂 （活性配合 活性配合剂 损耗率
试验 （ppm） 剂ppm） 的份数 （ppm/hr）
操作 0 0 0 1002
实例1 85 29 0.0058 982
实例2 148 51 0.0102 743
实例3 213 73 0.0146 534
实例4 425 146 0.0292 530
实例5 851 293 0.0586 480
表1的数据表明了以低浓度（每百万分子一）添加剂可以达到有效的降解抑制，这意味着抑制过程不同于S.N.831969所公开的抑制剂，在S.N.831969中要求相对高的主要净化剂的浓度（例如重量的5%），表1还表示了共聚物的高浓度在进一步减少降解方面有最小的影响。
实例6和7
以具有百分之9.5摩尔的丙烯酸（JayflocTM808）的中等电荷密度的聚丙烯酰胺-丙烯共聚物重复作实例1至5，其结果列于表2。
操作2
以硫代硫酸钠作为抑制剂重复操作1，这是一种已知的在US4，622，212中介绍过的抑制剂，其结果示于表2。
表2
试验 添加剂 添加剂 每份Fe的 Na3HEDTA
（ppm） （活性配合剂） 活性配合剂 损耗率
ppm 的份数 （ppm/hr）
实例7 24 16 0.003 594
实例8 54 36 0.007 386
操作2 67，714 67，714 13.5 510
表2的数据表明了较小量的中等电荷密度聚合物的抑制作用比小电荷密度材料更有效。而且，操作也表明就聚丙烯酰胺-丙烯酸共聚物而言，为了得到相同的效果必须使用高于2000倍的硫代硫酸盐。
Claims (8)
1、一种从流体中除去H2S的方法，包括：
A)在接触区内，所述的流体流与含有下列成分的水溶液接触
(1)铁(Ⅲ)螯合物
(2)含有磺基，羧基或它们的混合物的水溶阴离子聚合物稳定所述的螯合物，
在所述的溶液中铁螯合物还原为铁(Ⅱ)螯合物，产生净化气流和硫化颗粒。
B)在氧化区内再生所述的还原铁螯合物，
C)至少除去一部分所述的硫化颗粒，
D)再循环所述的再生铁螯合物至所述的接触区。
2、根据权利要求1所述的方法，其特征在于所述的流体是地热流。
3、根据权利要求1所述的方法，其特征在于所述的流体是酸气流，
4、根据权利要求1所述的方法，其特征在于所述的聚合物是适量水溶甲基丙烯酰胺和/或异丁烯酸聚合物。
5、根据权利要求1所述的方法，其特征在于所述的水溶液是
（Ⅰ）在螯合形态下，铁的重量的0.1至5.0%，
（Ⅱ）水溶阴离子聚合物的百万分之0.1至10000，这些聚合物是
（1）聚丙烯酸或聚异丁烯酸或它们的盐，
（2）部分水解了的聚丙烯酰胺或聚甲基丙烯酰胺，
（3）丙烯酸或异丁烯酸或它们的盐和丙烯酰胺或甲基丙烯酰胺的共聚物。
（4）乙烯基磺酸或它的盐和丙烯酰胺或甲基丙烯酰胺的共聚物，
（5）2-丙烯酰基酰氨基-2-甲基-丙烷磺酸盐和丙烯酸或异丁烯酸盐及丙烯酰胺或甲基丙烯酰胺的三元共聚物。
6、一种用于从气流中除去硫化氢的水溶液，包括：
A）被螯合的铁（Ⅲ）的重量的百分之0.1至5.0，
B）含有磺基，羧基或它们的混合物的水溶阴离子聚合物的百万分之0.1至10000，
7、根据权利要求6所述的水溶液，其特征在于该可溶阴离子聚合物是甲基丙烯酰基和/或异丁烯酸聚合物。
8、根据权利要求6所述的水溶液，其特征在于水溶阴离子聚合物是
1）聚丙烯酸或聚异丁烯酸或它们的盐，
2）部分水解了的聚丙烯酰胺或聚甲基丙烯酰胺，
3）丙烯酸或异丁烯酸或它们的盐和丙烯酰胺或甲基丙烯酰胺的共聚物，
4）乙烯基磺酸或它的盐和丙烯酰胺或甲基丙烯酰胺的共聚物，
5）2-丙烯酰基酰氨基-2-甲基-丙烷磺酸盐和丙烯酸或异丁烯酸盐及丙烯酰胺或甲基丙酰胺的三元共聚物。
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| Application Number | Priority Date | Filing Date | Title |
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| US23802488A | 1988-08-29 | 1988-08-29 | |
| US238,024 | 1988-08-29 |
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| CN1040744A true CN1040744A (zh) | 1990-03-28 |
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| US (1) | US5338778A (zh) |
| JP (1) | JPH03500986A (zh) |
| CN (1) | CN1040744A (zh) |
| AU (1) | AU617534B2 (zh) |
| CA (1) | CA1336511C (zh) |
| DK (1) | DK105590A (zh) |
| GB (1) | GB2224499B (zh) |
| MX (1) | MX172061B (zh) |
| NL (1) | NL8902171A (zh) |
| NO (1) | NO178288C (zh) |
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| WO (1) | WO1990001984A1 (zh) |
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| CN1119307C (zh) * | 2000-01-01 | 2003-08-27 | 罗富源 | 从林化杂酚中提取天然愈创木酚的方法 |
| CN116059812A (zh) * | 2022-12-07 | 2023-05-05 | 成都华阳兴华化工有限公司 | 一种络合铁离子脱硫剂的合成方法 |
| CN118454439A (zh) * | 2024-05-17 | 2024-08-09 | 河北络合科技有限公司 | Mdea法脱硫解析气用络合铁脱硫剂及其制备方法与使用方法 |
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| US5428621A (en) * | 1992-09-21 | 1995-06-27 | Sundisk Corporation | Latent defect handling in EEPROM devices |
| US5508014A (en) * | 1993-10-05 | 1996-04-16 | Gas Research Institute, Inc. | Regeneration of liquid redox systems using Thiobacillus ferrooxidans |
| US6353554B1 (en) | 1995-02-27 | 2002-03-05 | Btg International Inc. | Memory apparatus including programmable non-volatile multi-bit memory cell, and apparatus and method for demarcating memory states of the cell |
| US5989513A (en) * | 1995-07-28 | 1999-11-23 | Gas Research Institute | Biologically assisted process for treating sour gas at high pH |
| US5756852A (en) * | 1996-10-15 | 1998-05-26 | Barton; Derek H. R. | Co-oxidation of H2 S and saturated hydrocarbons |
| FR2771951B1 (fr) * | 1997-12-05 | 2001-08-03 | Inst Francais Du Petrole | Procede de regeneration d'une solution aqueuse contenant des ions ferreux ou ferriques avec de l'eau oxygenee |
| RU2179475C2 (ru) * | 1998-02-27 | 2002-02-20 | ГУП "Всероссийский научно-исследовательский институт углеводородного сырья" | Способ очистки природного газа от сероводорода |
| RU2193913C2 (ru) * | 2000-02-21 | 2002-12-10 | Общество с ограниченной ответственностью "ЛУКОЙЛ-ВолгоградНИПИморнефть" | Поглотительный раствор для очистки газов от сероводорода |
| KR100549544B1 (ko) * | 2001-04-25 | 2006-02-06 | 비앤이테크(주) | 황화수소 및 황화수소/아황산가스 동시 제거용 액상철착물 조성물 |
| RU2320398C2 (ru) * | 2006-04-13 | 2008-03-27 | Общество с ограниченной ответственностью Нефтегаз-Сталь Экспертно-научно-внедренческая компания ООО "НЕФТЕГАЗ-СТАЛЬ-ЭНВК" | Способ очистки углеводородной продукции от сероводорода |
| RU2320399C1 (ru) * | 2006-08-07 | 2008-03-27 | Общество с ограниченной ответственностью Нефтегаз-Сталь Экспертно-научно-внедренческая компания ООО "НЕФТЕГАЗ-СТАЛЬ-ЭНВК" | Способ очистки газов от сероводорода |
| RU2436620C1 (ru) * | 2010-07-01 | 2011-12-20 | Ахмед Ибрагим Шакер Салех | Способ очистки углеводородной продукции от кислых примесей |
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-
1989
- 1989-08-24 AU AU42082/89A patent/AU617534B2/en not_active Ceased
- 1989-08-24 JP JP1509366A patent/JPH03500986A/ja active Pending
- 1989-08-24 WO PCT/US1989/003666 patent/WO1990001984A1/en not_active Ceased
- 1989-08-25 CN CN89107762A patent/CN1040744A/zh active Pending
- 1989-08-28 NL NL8902171A patent/NL8902171A/nl active Search and Examination
- 1989-08-28 SE SE8902858A patent/SE8902858L/xx not_active Application Discontinuation
- 1989-08-28 MX MX017329A patent/MX172061B/es unknown
- 1989-08-28 CA CA000609571A patent/CA1336511C/en not_active Expired - Fee Related
- 1989-08-29 GB GB8919542A patent/GB2224499B/en not_active Expired - Fee Related
-
1990
- 1990-04-27 NO NO901879A patent/NO178288C/no unknown
- 1990-04-27 DK DK105590A patent/DK105590A/da not_active Application Discontinuation
- 1990-10-03 US US07/592,402 patent/US5338778A/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1119307C (zh) * | 2000-01-01 | 2003-08-27 | 罗富源 | 从林化杂酚中提取天然愈创木酚的方法 |
| CN116059812A (zh) * | 2022-12-07 | 2023-05-05 | 成都华阳兴华化工有限公司 | 一种络合铁离子脱硫剂的合成方法 |
| CN118454439A (zh) * | 2024-05-17 | 2024-08-09 | 河北络合科技有限公司 | Mdea法脱硫解析气用络合铁脱硫剂及其制备方法与使用方法 |
| CN118454439B (zh) * | 2024-05-17 | 2025-01-21 | 河北络合科技有限公司 | Mdea法脱硫解析气用络合铁脱硫剂及其制备方法与使用方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1990001984A1 (en) | 1990-03-08 |
| NO178288B (no) | 1995-11-20 |
| GB8919542D0 (en) | 1989-10-11 |
| AU4208289A (en) | 1990-03-23 |
| GB2224499B (en) | 1992-03-25 |
| SE8902858D0 (sv) | 1989-08-28 |
| NL8902171A (nl) | 1990-03-16 |
| NO178288C (no) | 1996-02-28 |
| SE8902858L (sv) | 1990-03-01 |
| MX172061B (es) | 1993-12-01 |
| DK105590D0 (da) | 1990-04-27 |
| JPH03500986A (ja) | 1991-03-07 |
| NO901879L (no) | 1990-06-13 |
| GB2224499A (en) | 1990-05-09 |
| US5338778A (en) | 1994-08-16 |
| AU617534B2 (en) | 1991-11-28 |
| CA1336511C (en) | 1995-08-01 |
| NO901879D0 (no) | 1990-04-27 |
| DK105590A (da) | 1990-04-27 |
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