CN105377394A - 双相不锈钢在氨汽提或自汽提尿素设备的汽提塔中的应用以及改造该尿素设备的方法 - Google Patents
双相不锈钢在氨汽提或自汽提尿素设备的汽提塔中的应用以及改造该尿素设备的方法 Download PDFInfo
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- 239000004202 carbamide Substances 0.000 title claims abstract description 33
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims description 36
- 229910001039 duplex stainless steel Inorganic materials 0.000 title abstract 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 33
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- 229910001220 stainless steel Inorganic materials 0.000 claims description 27
- 239000010935 stainless steel Substances 0.000 claims description 27
- 229910000831 Steel Inorganic materials 0.000 claims description 15
- 239000010959 steel Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 3
- 230000009466 transformation Effects 0.000 claims description 3
- 239000011552 falling film Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 239000012071 phase Substances 0.000 description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- YOWAEZWWQFSEJD-UHFFFAOYSA-N quinoxalin-2-amine Chemical class C1=CC=CC2=NC(N)=CN=C21 YOWAEZWWQFSEJD-UHFFFAOYSA-N 0.000 description 3
- 239000007991 ACES buffer Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241000283984 Rodentia Species 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- -1 and wherein Substances 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
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Abstract
在用于尿素合成的氨汽提或自汽提设备中，公开了一种壳管式汽提塔，具有由根据UNS？S32906的双相不锈钢29Cr-6.5Ni-2Mo-N或根据UNS？S32808的双相不锈钢27Cr-7.6Ni-1Mo-2.3W-N制得的一束管。还公开了改造尿素生产装置的方法，包括改造氨汽提设备、自汽提设备以及常规全循环设备，其中所述双相不锈钢是用于汽提塔的管。
Description
技术领域
本发明涉及制造或改造氨汽提和自汽提尿素设备。
背景技术
尿素合成工艺及其相关设备的概述可以在乌尔曼工业化学百科全书，德国威利出版社，卷A27(Ullmann’sEncyclopediaofIndustrialChemistry,Wiley-VCHVerlag,vol.A27)中找到。
汽提工艺在20世纪60年代被引入，目前在全球的尿素生产中占主要地位。在汽提工艺中，离开反应器的合成溶液在基本上与反应器相同的高压条件下进行加热。因此，该氨基甲酸铵在液相中分解为氨和二氧化碳，且部分释放出的氨和二氧化碳由液相转变为气相。从该汽提塔收集的气相，含有未转化的氨和二氧化碳，被冷凝并循环到该反应器中。
氨汽提工艺采用氨作为汽提剂，以促进上述工艺。自汽提工艺未采用汽提剂，溶液的汽提仅通过热量供应来实现。
氨汽提工艺和自汽提工艺是众所周知的，用其开发者的名字也被统称为斯纳姆普罗盖提(Snamprogetti)工艺。由于热量导致尿素溶液的汽提，自汽提工艺也被称为热汽提工艺。
一个不同的汽提工艺是CO2汽提工艺，其中气态二氧化碳被用作汽提剂。斯塔米卡邦(Stamicarbon)工艺和ACES工艺是公知的CO2汽提工艺的例子。
本发明涉及斯纳姆普罗盖提(Snamprogetti)工艺和相关设备。在本说明书和权利要求书中，任何对自汽提工艺或设备的引用须同样地被作为对氨汽提工艺或设备的引用，反之亦然。
自汽提尿素装置主要包括高压合成回路、中压段和低压回收段。高压合成回路通常包括合成反应器、蒸汽加热的汽提塔和卧式釜冷凝器，冷凝器基本上在相同的压力下操作，通常约为140至160巴。尿素水溶液离开反应器后，包括氨和未转化的氨基甲酸铵，被汽提获得含有氨和CO2的气相，被冷凝于高压冷凝器并循环到所述反应器中。以下中压段和低压段分解未反应的氨基甲酸盐并从离开高压区的尿素水溶液中回收氨。
合成回路提供高压、高温和存在腐蚀性溶液的组合。特别是，氨基甲酸铵被认为是对钢最有侵蚀性的。由于汽提管在高温高压、高浓度的氨基甲酸盐和低氧气下操作，并且汽提管是最关键的部件之一，因此，合适的材料的选择是一个挑战。
在过去很长一段时间里氨汽提和自汽提设备采用钛汽提管。为了克服钛管内部的侵蚀问题，我们引入了双金属管，包括由奥氏体不锈钢制成的外部管和由锆制成的内部管。这种观念的进一步发展导致全锆管或双金属钛-锆(Ti-Zr)管的产生。在这方面，EP-A-1577632公开了由钛制成的管，或由涂覆有锆层或锆合金层的钛合金制成的管，适用于斯纳姆普罗盖提(Snamprogetti)尿素设备的汽提管中。
与此相反，CO2汽提工艺已使用特殊不锈钢，包括高合金不锈钢和双相不锈钢。该双相不锈钢具有既显示铁素体又显示奥氏体的两相结构的特点，并且通常具有高的铬含量。
总之，到目前为止现有技术已经促使CO2汽提设备的汽提管使用优质钢，和用于氨汽提或自汽提设备的管的更复杂的解决方案(钛管、锆或双金属管)。
由于斯纳姆普罗盖提(Snamprogetti)设备占世界尿素生产能力大部分份额，因此提供一种改善其性能的有效方法是有动机的，特别是改造现有的设备。本发明正面临这一问题。
发明内容
申请人已经惊奇地发现某些双相不锈钢也可成功地用在自汽提和氨汽提设备中用于制造汽提塔的管。根据本发明，采用以下双相不锈钢中的一种：
A)钢，即29Cr-6.5Ni-2Mo-N，其也由ASME规范2295-3和UNSS32906指定，
或者：
B)DP28WTM钢，即27Cr-7.6Ni-1Mo-2.3W-N，其也由ASME规范例2496-1和UNSS32808指定。
根据公知的标准给出合适的材料的上述指定，这是本领域技术人员所熟悉的，即：DIN标准命名法、ASME规范和UNS(UnifiedNumberingSystem，统一编号系统)指定。
根据所述A)选项的双相不锈钢，即钢，优选地具有下列组成(质量％)：
C:最大值0.05,
Si:最大值0.8
Mn:0.3-4.0
Cr:28-35,
Ni:3-10,
Mo:1.0-4.0
N:0.2-0.6,
Cu:最大值1.0
W:最大值2.0
S:最大值0.01
Ce:0-0.2。
所述铁素体含量按体积计优选为30-70％，更优选为30-55％。
更优选地，根据A)选项的所述钢含有(重量％)：C最大值为0.02，Si最大值为0.5，Cr29-33，Mo1.0-2.0，N0.36-0.55，Mn0.3-1.0。
根据B)选项的所述双相不锈钢，即DP28WTM钢，优选地具有下列组成(质量％)：
C：小于或等于0.03，
Si：小于或等于0.5，
Mn：小于或等于2，
P：小于或等于0.04，
S：小于或等于0.003，
Cr：大于或等于26，但小于28，
Ni：6-10，
Mo：0.2-1.7，
W：大于2，但不超过3，
N：大于0.3，但不超过0.4，
剩余部分由Fe和杂质构成，其中，Cu作为杂质的含量不超过0.3％。
更优选地，根据B)选项的所述钢包括：27-27.9％的铬(Cr)；7％-8.2％的镍(Ni)；0.8％-1.2％的钼(Mo)；2％-2.5％的钨(W)；0.3-0.4％的氮(N)。
上述所有的百分数都是以质量计。
如上所述，双相不锈钢在尿素设备领域中的应用在相关的现有技术和仅结合CO2汽提工艺的文献中被提及，CO2汽提工艺例如上述的斯塔米卡邦(Stamicarbon)或ACES工艺。
应当指出的是，与CO2汽提设备的汽提管相比，斯纳姆普罗盖提(Snamprogetti)尿素设备的汽提塔的管在较高的温度下操作。通常地，氨汽提或自汽提设备的汽提塔在约205℃或以上(例如200-210℃)的出口温度下操作，而CO2汽提设备的汽提塔在约160℃的出口温度下操作。此外，供给到汽提塔底部的CO2含有O2，是用于钢表面防腐蚀的钝化剂。到目前为止，由于上述差异，双相不锈钢用于氨汽提和自汽提尿素设备的汽提塔中被认为是不恰当的。
与上述偏见相比，申请人已发现，根据上述化学要求，某些双相不锈钢可用于制造氨汽提和自汽提尿素设备的汽提管。
按照上述情况，本发明的第一方面是一种壳管式汽提塔，在用于尿素合成的氨汽提或自汽提设备中应用，其中所述汽提塔包括一个壳和一束管，并被设置成通过加热以及可选地通过氨作为汽提介质所述管将供应的氨基甲酸酯溶液提供至所述管，并且其中所述汽提塔的管是由所述双相不锈钢制成。
在使用中，所述汽提塔的管束被供给反应器流出物(尿素溶液)在管内流动。汽提工艺的热量来自，例如，被供给壳程的热蒸汽，从而加热该管束。
优选地，所述汽提塔是降膜式竖直汽提塔。在这种情况下，所述尿素溶液以形成管内液体膜向下流动的方式供给，而汽提的气相，包括氨和二氧化碳，逆流流经管的中心部分，并在汽提塔的顶部被收集。管外流动的热蒸汽提供必需的热量，以分解包含于该溶液中的氨基甲酸酯。
特别优选地，含氧(O2)流在汽提塔底部供给，以为了保护该管而提供钝化剂。这是可以实现的，例如，通过专用的空气流，或更优选地通过在反应器顶部气/液分离。当钝化氧被供给到反应器中时，可以使用第二实施例。从反应器顶部回收的气态流出物包括未反应的二氧化碳和氨以及一些钝化氧。因此，所述流出物可被用于保护汽提塔。
本发明的另一个方面是一种设备，根据氨汽提或热汽提工艺操作用于尿素的合成。该设备包括高压合成回路，该高压合成环路包括合成反应器、壳管式汽提塔和冷凝器，其中所述汽提塔包括由根据上述选项的双相不锈钢制成的管。
本发明的另一个方面涉及对现有的氨汽提和自汽提尿素装置的改造，采用根据上述选项的双相不锈钢作为汽提塔的管的材料。例如，带有由上述钢中的一种钢制成的管的新的汽提塔可以替代旧的常规汽提塔(带有由常规钢的管、或钛管或双金属管)被安装。在适当的时候，汽提塔的壳可以被维修，仅以新的由双相不锈钢制成的管替换旧管。
本发明的另一种应用是根据上述选项在汽提塔中将常规的全循环回路改造为利用双相不锈钢的现代自汽提工艺。术语全循环(total-recycle)表示未经汽提的旧设备，其中所有未转化的二氧化碳伴随水溶液被回收。
一种改造非汽提的全循环尿素设备的方法，例如，包括高压壳管式汽提塔的供给，其基本上在现有反应器的压力下操作，以及冷凝器的供给，以形成高压回路。因此，一个传统的全循环设备被转化成一个更有效的汽提设备。根据上述选项，新的汽提塔具有由双相不锈钢制成的管。
本发明的另一个方面是一种根据自汽提或氨汽提工艺的尿素合成工艺，包括在壳管式汽提塔中汽提反应器流出物的步骤，其中所述汽提塔的管是由根据上述选项的双相不锈钢制成。
Claims (12)
1.一种壳管式汽提塔，在用于尿素合成的氨汽提设备或自汽提设备中的应用，其中所述汽提塔包括一个壳和一束管，并被设置成通过加热以及可选地通过氨作为汽提介质所述管将供应的氨基甲酸酯溶液提供至所述管，其特征在于，所述管是由下列双相不锈钢中的一种制成：
A)钢，即29Cr-6.5Ni-2Mo-N，其也由ASME规范2295-3和UNSS32906指定，
或者：
B)DP28WTM钢，即27Cr-7.6Ni-1Mo-2.3W-N，其也由ASME规范例2496-1和UNSS32808指定。
2.根据权利要求1所述的汽提塔，其特征在于，所述汽提塔在温度约为205℃、压力为140-160巴下操作。
3.根据上述任一权利要求所述的汽提塔，其特征在于，所述汽提塔为降膜式汽提塔。
4.一种根据氨汽提或热汽提工艺的尿素合成设备，包括高压合成回路，所述高压合成回路包括合成反应器、壳管式汽提塔和冷凝器，其特征在于，所述汽提塔是根据权利要求1-5任一所述的汽提塔。
5.根据权利要求4所述的设备，其特征在于，所述设备包括设置成在所述汽提塔底部供给含氧流的供给线。
6.根据权利要求5所述的设备，其特征在于，所述含氧流的供料管线为指向所述汽提塔底部的专用空气供给线。
7.根据权利要求6所述的设备，其特征在于，所述含氧流的供给线为取自在所述回路的合成反应器顶部的气/液分离器的反应流出物。
8.根据权利要求1的选项A)或选项B)所述的双相不锈钢在制造氨汽提尿素设备或自汽提尿素设备的汽提塔的管束中的应用。
9.一种改造氨汽提或热汽提尿素设备的方法，其特征在于，双相不锈钢供给所述设备的壳管式汽提塔的管的应用，所述双相不锈钢是根据权利要求1所述的选项A)或选项B)的钢。
10.根据权利要求9所述的设备，其特征在于，现有汽提塔的原管被替换为新的由双相不锈钢制成的管。
11.一种改造非汽提的全循环尿素设备的方法，其特征在于，高压壳管式汽提塔的供给，所述汽提塔包括由双相不锈钢制成的管，所述双相不锈钢是根据权利要求1所述的选项A)或选项B)的钢。
12.一种根据自汽提或氨汽提工艺的尿素合成工艺，包括在壳管式汽提塔中汽提反应器流出物的步骤，其特征在于，所述汽提塔的管是由根据权利要求1所述的选项A)或选项B)的双相不锈钢制成。
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| EP13167242.0 | 2013-05-10 | ||
| EP20130167242 EP2801396A1 (en) | 2013-05-10 | 2013-05-10 | Use of duplex stainless steel in an ammonia-stripping of urea plants |
| PCT/EP2014/059053 WO2014180761A1 (en) | 2013-05-10 | 2014-05-05 | Use of duplex stainless steel in an ammonia-stripping of urea plants |
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| EP (2) | EP2801396A1 (zh) |
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| CA2991658C (en) * | 2015-07-20 | 2023-12-19 | Sandvik Intellectual Property Ab | Duplex stainless steel and formed object thereof |
| UA124949C2 (uk) * | 2015-07-20 | 2021-12-15 | Стамікарбон Б.В. | Дуплексна нержавіюча сталь та її застосування |
| AU2018366077B2 (en) | 2017-11-10 | 2021-07-08 | Stamicarbon B.V. | Urea production process and plant |
| PL3502293T3 (pl) | 2017-12-22 | 2020-11-02 | Saipem S.P.A. | Zastosowania dupleksowych stali nierdzewnych |
| JP2022539597A (ja) | 2019-07-05 | 2022-09-12 | スタミカーボン・ベー・フェー | 尿素プラントのフェライト鋼部品 |
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| EP2994208A1 (en) | 2016-03-16 |
| RU2654018C2 (ru) | 2018-05-15 |
| US20160082408A1 (en) | 2016-03-24 |
| EP2801396A1 (en) | 2014-11-12 |
| CA2910373A1 (en) | 2014-11-13 |
| CA2910373C (en) | 2021-02-16 |
| RU2015152849A (ru) | 2017-06-16 |
| WO2014180761A1 (en) | 2014-11-13 |
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