CN1311754A - 烃原料的自热转化方法 - Google Patents
烃原料的自热转化方法 Download PDFInfo
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 19
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 19
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000002453 autothermal reforming Methods 0.000 title description 2
- 239000007789 gas Substances 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 230000008676 import Effects 0.000 claims 1
- 239000000376 reactant Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 229940105305 carbon monoxide Drugs 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 25
- 229910052799 carbon Inorganic materials 0.000 description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- 238000012360 testing method Methods 0.000 description 14
- 235000019504 cigarettes Nutrition 0.000 description 12
- 239000003345 natural gas Substances 0.000 description 10
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- 238000006243 chemical reaction Methods 0.000 description 8
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- 238000013459 approach Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- 238000004442 gravimetric analysis Methods 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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Abstract
制造富含氢和/或一氧化碳气体的方法,该方法包括在蒸汽存在下使烃原料与含氧的反应剂物流进行部分氧化的步骤,其中蒸汽在烃原料中的含量高于在含氧反应剂物流中的含量。
Description
本发明涉及在不会形成烟灰情况下的烃原料的自热转化(ATR)。
在自热转化过程中，烃原料在燃烧器的燃烧区通过火焰反应与低于化学计量量的氧发生燃烧反应，接着，在蒸汽转化催化剂的固定床中。经部分燃烧的原料进行蒸汽转化。烃的低于化学计量量的燃烧会形成不希望有的烟灰。采用专门设计的燃烧器和控制ATR过程的操作条件，可避免烟灰的形成。在某些操作条件范围内，会在自热反应器的火焰中产生烟灰。当通过ATR反应的蒸汽量相对于其它组分低于一定临界值时，就会在反应原料中形成烟灰。蒸汽的限量可用临界蒸汽量与碳量之比率来表示，即以蒸汽的摩尔流速与烃供料中碳的摩尔流速而算得。烃原料可以是天然气或包括LPG、丁烷、石脑油等在内的其它烃类。碳的摩尔流速是以烃摩尔流速乘以烃中碳的含量而算得。燃烧器喷嘴的设计会对临界蒸汽用量与碳含量之比率产生影响。一种适用ATR的燃烧器已公开在美国专利5496170中。
不会导致形成烟灰的操作条件的实例已汇总于Christensen和Primdahl写的论文(《烃加工》，1994年3月，39-46页)中。公开在该论文中的条件已列于表1中。由于Christensen和Primdahl实验中采用的较小中试装置有热损失，因此绝热的ATR出口温度会高于表1所列温度。这就意味着，如果热损失可忽略不计的大装置是在严格相同的条件下运行的话，那么ATR出口温度会接近于绝热ATR出口的温度。
有利的是，该方法是在低的蒸汽用量与碳含量之比率下操作的，因为低的蒸汽用量与碳含量之比率可降低ATR车间的投资和减少生产车间必需的能量消耗。此外，低的蒸汽用量与碳含量之比率可使供制造富含CO气体的生成的合成气组成最优化，其中富含CO气体可用于例如甲醇或二甲醚的合成以及Fisher-Tropsh过程。
供给ATR的物料是分成两股独立的物流送入燃烧器中的。一股物流含氧和蒸汽。另一股物流含烃和蒸汽以及非必需的氢和/或二氧化碳。两股物流顺流(downstream)在燃烧器中混合并发生燃烧反应。
业已发现，临界蒸汽用量与碳含量之比率随蒸汽在氧和烃物流中的分配而定。当氧物流中蒸汽量下降时，临界蒸汽用量与碳含量之比率就下降。
本发明说明
根据上述研究结果，本发明提供制备富氢和/或一氧化碳气体的方法，该方法包括在蒸汽存在下，使烃原料与含氧反应剂物流进行部分氧化的步骤，其中蒸汽在烃原料中的含量高于在含氧反应剂物流中的含量。
本发明方法可在含氧物流与含烃物流之间的蒸汽分配相等的条件下，蒸汽用量与碳含量之比率在较临界蒸汽用量/碳含量之比率为低的情况下实施。由于本发明降低了与临界蒸汽用量与碳含量之比率的差距，因而可在操作条件发生变化(如物料供料受到干扰)时，降低形成烟灰的可能性。
下面实施例是用来说明本发明方法的，含氧物流中蒸汽含量一直降至5％，然而，在更低的蒸汽浓度下，该方法也是适用的。
实施例
所采用的试验性装置组成为向ATR反应器供给物流的系统、ATR反应器本身以及用于产物气体后处理的设备。
原料物流组成为天然气、蒸汽、氧气及氢气。所有气体都经压缩至操作压力并预热至操作温度。天然气在进入ATR反应器前先进行脱硫。将原料气混合成两股物流并送入ATR的燃烧器中。第一股含天然气、氢气和蒸汽的物流被加热至500℃。第二股含氧气和蒸汽的物流被加热至220℃。
在ATR反应器中，进行低于化学计量量的燃烧反应以及随后的催化蒸汽转化和转移反应。以气相色谱法对入口和出口的气体成分进行分析。产物气体与转化反应和转移反应间存在平衡关系。
在ATR反应器下流，使反应气体冷却，以使产物气体中大部分蒸汽冷凝。在上述反应过程中产生的任何烟灰会聚集在冷凝液中。对冷凝液进行重量分析和光谱分析。
为了说明根据本发明的蒸汽分配对临界蒸汽用量与碳含量之比率的影响，进行了下列试验。所用的烃是天然气。天然气的组成列于表2中。
表2
| 天然气的组成 | |
| 组分 | 摩尔分数％ |
| N2 | 0.45 |
| CO2 | 1.20 |
| CH4 | 95.36 |
| C2 | 2.22 |
| C3 | 0.45 |
| C4 | 0.23 |
| C5 + | 0.08 |
每次试验从富含蒸汽端接近临界蒸汽用量与碳含量之比率来进行。试验是在足够高的蒸汽流速以保证不会形成烟灰的条件下开始。然后将蒸汽流速逐渐降低至蒸汽与碳之比率为约0.03。使体系稳定后，测定冷凝液中烟灰含量。如果冷凝液中仍没有烟灰的话接着进行下一步。术语“不形成烟灰条件”是指在该反应条件下所形成的烟灰可忽略不计。在临界蒸汽用量与碳含量之比率条件下形成的烟灰量为约3-5ppm。
表3列出了在不同的蒸汽分配和在两种不同温度下的临界蒸汽用量与碳含量之比率。在以下试验中，天然气流速为100Nm3/小时，氢气为3Nm3/小时。100Nm3/小时的天然气相当于为103Nm3/小时的碳流速。调整氧气流速至达到所需的操作温度，其流速可在56-61Nm3/小时不等。
由于较小中试装置的热损失，因此绝热ATR出口温度会高于表3所列的温度。这就意味着如果热损失可忽略不计的大装置在严格相同的条件下操作的话，那么ATR出口温度会接近于绝热ATR出口的温度。
表3
| 临界蒸汽用量与碳含量之比率随蒸汽分配和温度的变化，压力为24.5巴 | |||||||
| 试验号 | O2/C | 含氧物流中蒸汽流速 | 含氧物流中蒸汽浓度 | 含天然气物流中蒸汽流速 | 临界S/C | ATR出口气体温度 | 绝热出口温度 |
| Nm3/h | mol％ | Nm3/h | ℃ | ||||
| 1.1 | 0.59 | 25 | 29 | 67 | 0.89 | 970 | 1032 |
| 1.2 | 0.57 | 8 | 12 | 61 | 0.67 | 971 | 1024 |
| 1.3 | 3 | 约5 | 61 | 0.62 | (971) | ||
| 2.1 | 0.59 | 18 | 24 | 22 | 0.39 | 1032 | 1105 |
| 2.2 | 0.58 | 4 | 6 | 31 | 0.34 | 1030 | 1102 |
以气相色谱法测定表3所列试验中ATR反应器的产物的组成。所选择的气体组成列于表4。所列气体组成以干摩尔％表示，即不包括蒸汽的气体组分的摩尔组成。
表4
| 表3试验的产物气体的组成(干摩尔％) | |||||
| 试验号 | H2 | N2 | CO | CO2 | CH4 |
| ％ | ％ | ％ | ％ | ％ | |
| 1.1 | 64.6 | 0.3 | 25.8 | 7.9 | 1.4 |
| 1.2 | 64.2 | 0.3 | 27.0 | 6.5 | 2.0 |
| 2.1 | 64.1 | 0.2 | 29.9 | 4.7 | 1.1 |
| 2.2 | 63.4 | 0.2 | 30.7 | 4.3 | 1.4 |
表3所列数据清楚地表明，蒸汽分配对临界蒸汽用量与碳含量之比率有影响。试验号1.1的临界蒸汽用量与碳含量之比率较试验号1.3的临界蒸汽用量与碳含量之比率高44％。在试验号1.1和试验号1.3中，含氧物流中蒸汽浓度分别为29％和5％。温度升高时也有类似影响，但影响不这么明显。试验号2.1中的临界蒸汽用量与碳含量之比率较试验号2.2中的临界蒸汽用量与碳含量之比率高15％，其中在含氧物流中的蒸汽浓度分别为24％和6％。
Claims (4)
1．制造富含氢和/或一氧化碳气体的方法，该方法包括在蒸汽存在下使烃原料与含氧反应剂物流进行部分氧化的步骤，其中蒸汽在烃原料中的含量高于在含氧反应剂物流中的含量。
2．根据权利要求1的方法，其中部分氧化步骤是在处于自热反应器顶部的燃烧器中进行的。
3．根据权利要求1的方法，其中低于总量1/3的蒸汽是与含氧物流一起导入的。
4．根据权利要求1的方法，其中含氧物流中蒸汽含量低于12％。
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| CN105820036A (zh) * | 2014-12-17 | 2016-08-03 | 普莱克斯技术有限公司 | 使用部分氧化生产甲醇的方法和系统 |
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| DK173745B1 (da) * | 1998-08-27 | 2001-09-03 | Topsoe Haldor As | Fremgangsmåde til autotermisk reforming af carbonhydridmateriale |
| JP4953546B2 (ja) * | 2000-09-20 | 2012-06-13 | 国際石油開発帝石株式会社 | 緻密酸素選択透過セラミックス膜を用いるメタン部分酸化方法 |
| US8394154B2 (en) | 2007-12-28 | 2013-03-12 | Texaco Inc. | Counter-current oxidation and steam methane reforming process and reactor therefor |
| US7989511B2 (en) | 2008-05-21 | 2011-08-02 | Texaco Inc. | Process and apparatus for synthesis gas and hydrocarbon production |
| DE102015210803A1 (de) * | 2015-06-12 | 2016-12-15 | Thyssenkrupp Ag | Festlegung von Druck, Temperatur und S/C-Verhältnis für einen rußfreien ATR-Betrieb |
| KR20210128468A (ko) * | 2019-02-18 | 2021-10-26 | 스카이어, 아이엔씨. | 수소를 회수하고, 탄소 화합물을 유용한 유기 생성물로 전환시키기 위한 방법 및 시스템 |
| CA3127978A1 (en) | 2019-04-08 | 2020-10-15 | Haldor Topsoe A/S | Chemical synthesis plant |
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| US4822521A (en) * | 1983-06-09 | 1989-04-18 | Uop | Integrated process and apparatus for the primary and secondary catalytic steam reforming of hydrocarbons |
| US4666680A (en) * | 1984-01-30 | 1987-05-19 | Fluor Corporation | Autothermal production of synthesis gas |
| US4861351A (en) * | 1987-09-16 | 1989-08-29 | Air Products And Chemicals, Inc. | Production of hydrogen and carbon monoxide |
| DE3902773A1 (de) * | 1989-01-31 | 1990-08-02 | Basf Ag | Verfahren zur herstellung von synthesegas durch partielle oxidation |
| DK168460B1 (da) * | 1991-12-06 | 1994-03-28 | Topsoe Haldor As | Hvirvelbrænder |
| US5411927A (en) * | 1992-08-14 | 1995-05-02 | Council Of Scientific & Industrial Research | Process of preparing composite catalysts for production of synthesis gas by oxidative conversion of methane or natural gas |
| US5358696A (en) * | 1993-12-01 | 1994-10-25 | Texaco Inc. | Production of H2 -rich gas |
| EP0936182A3 (en) * | 1998-02-13 | 2000-02-23 | Haldor Topsoe A/S | Method of soot-free start-up of autothermal reformers |
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| CN105820036B (zh) * | 2014-12-17 | 2020-12-29 | 普莱克斯技术有限公司 | 使用部分氧化生产甲醇的方法和系统 |
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| DE69927976D1 (de) | 2005-12-01 |
| EP1098838A1 (en) | 2001-05-16 |
| JP4154123B2 (ja) | 2008-09-24 |
| AU4904499A (en) | 2000-01-24 |
| ZA200007806B (en) | 2002-05-02 |
| WO2000001613A1 (en) | 2000-01-13 |
| NO20006713D0 (no) | 2000-12-29 |
| ES2251205T3 (es) | 2006-04-16 |
| NO20006713L (no) | 2001-03-02 |
| US6689294B1 (en) | 2004-02-10 |
| JP2002519293A (ja) | 2002-07-02 |
| DE69927976T2 (de) | 2006-04-20 |
| EP1098838B1 (en) | 2005-10-26 |
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