CN1124226C - 制备合成气的方法和反应器系统 - Google Patents
制备合成气的方法和反应器系统 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000000629 steam reforming Methods 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 210000000056 organ Anatomy 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims 1
- 238000001193 catalytic steam reforming Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000001131 transforming effect Effects 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
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Abstract
通过烃原料的催化蒸汽转化制备富氢和/或富一氧化碳气的方法,其中第一部分原料气流以并联于第二部分原料气流进行自热转化,第二部分原料气流在蒸汽转化催化剂存在下与从自热蒸汽转化来的热流出气和自蒸汽转化催化剂排出的蒸汽转化热流出气呈热传导关系而进行蒸汽转化,并在给第二部分原料气流中的蒸汽转化反应物供给热量之后,混合从自热蒸汽转化步骤和热交换蒸汽转化步骤的流出气。
Description
技术领域
本发明涉及通过烃原料的催化蒸汽转化制备氢和/或富一氧化碳合成气。具体地,本发明涉及通过在自热转化器(ATR)和热交换转化器中原料的并联蒸汽转化生产合成气的某些改进,其中一部分原料在ATR中被自热蒸汽转化而其余部分原料在热交换转化器中被转化。
背景技术
US 5011625公开了一种自热蒸汽转化方法,其中利用烃原料制造氨,更具体的是利用烃原料与蒸汽和氧化剂制造氨合成气。
发明内容
按本发明的方法,将在热交换转化器中催化蒸汽转化的这部分原料以与从ATR来的热转化流出气流和从蒸汽转化催化剂而来的蒸汽转化流出气流呈热传导关系通过转化器,催化剂安装于热交换转化器中。
在给有蒸汽转化催化剂存在的热交换转化器中进行的蒸汽转化反应物供给热量之后,将两股蒸汽转化流出气流混合。
当如上述本发明的方法通过热交换转化器之后从ATR和热交换反应器收集蒸汽转化流出气流时,在热交换反应器中装有催化剂的管和用于从反应器中排出蒸汽转化流出气流管之间的压差能保持在最低,因此,改善了管的腐蚀和尺寸稳定性,从而这些管子可以使用高耐化学性和比普通热交换转化器中要低的机械强度的材料来制造。
在本发明的方法中,安装在热交换反应器中的蒸汽转化催化剂可以是固定床或催化剂硬件形式,例如将催化剂以薄膜状涂敷于与反应原料相接触的金属表面上。
此外,本发明提供了一个用于上述方法的反应器系统,该反应器系统包括一台自热转化反应器和一台在反应器入口处并联相接而在自热反应器出口处串联相接的热交换反应器,其中热交换反应器至少装有一根具有内外管双管形式的转化器管,外管装有转化催化剂,内管适用于排出从外管来的蒸汽转化原料的流出气流。外管由与其有一定间隔的套管同轴围绕并适用于通过来自自热反应器的热蒸汽转化流出气流,在套管和外管之间的空间流通的热流出气流与外管的反应原料呈热传导关系,和在热交换反应器的下游,用以收集来自热交换反应器的流出气流的收集器。
在本发明的具体实施方案中,在热交换反应器中的转化催化剂以固定床形式施于内外管壁之间或以薄膜涂敷于外管的内壁和/或内管的外壁上。
附图说明
通过参见下述附图的说明对上述方法和反应器体系将会更清楚,其中该附图表明本发明的具体实施方案的简单流程图。
将经脱硫和预热的天然气分成气流1和2并与过热蒸汽流3和4混合以得到原料流5(由气流1和3相混合的)进入自热转化器(ATR)和原料流6通入热交换转化器(HTCR)。在ATR中,将原料流5在含Ni催化剂上与氧化剂气流7(氧、富氧空气或空气)相反应以生成含H2,CO,CO2、残量CH4和蒸汽,以及含于原料流1和7中的某些惰性气(N2和Ar)的混合物8。在HTCR中,原料流6在由合适的耐温和耐腐材料制成的内(卡口)管和外管之间环形空间的含Ni催化剂上进行反应,在HTCR-催化剂上吸热反应的热量,由来自ATR的出气8和在HTCR中含催化剂的环形空间的外壁之间的热交换提供,也由来自在HTCR中的催化剂床的出气9和HTCR中含催化剂的环形空间的内壁之间的热交换提供。给HTCR提供热量之后,两股产品物流8和9混合成最终的产品物流10。由于选取原料流5、6和7的合适组成、流量和条件,合适的ATR和HTCR操作条件以及合适的ATR和HTCR的机械设计,因而可以得到预选性能的最终产品物流10。
具体实施方式
实例
将550℃和40×105帕斯卡(40巴)的1000kmol CH4分成750kmol物流(物流1)和250kmol物流(物流2)。将物流1与550℃和40×105帕斯卡(40巴)的1132kmol蒸汽(物流3)相混合并与430kmol的氧(物流7)一道用作ATR的原料(物流5)。ATR含有一个专用的混合燃烧器和促进反应以生成产物流8的常规含Ni蒸汽转化催化剂,产物流以1000℃温度离开ATR。物流2与550℃和40×105帕斯卡(40巴)的500kmol蒸汽(物流4)相混合,其混合物(物流6)用作HTCR的原料。HTCR含有100根并联的管子,每根12m长并由dy/di=130.0mm/122.3mm的外管和dy/di=48.3mm/40.9mm的内(卡口)管构成。外管和内管之间的环形空间填装着常规的含Ni催化剂。原料气6向下流过催化剂充填的环形空间被转化和加热。产品物气9以928℃温度离开催化剂并向上流过内(卡口)管,在这时它由于与催化剂的热交换温度冷却到638℃,因而提供了部分所需的热量。其余所需热量由外管和来自ATR沿外管壁向上流动并被冷却到600℃的产品气8之间的热交换提供。冷却以后,产品气8和9混合成含2129kmol H2,656kmol CO、254kmol CO2和90KmolCH4的最终产品气。这种气例如适用于用费-托合成法生产MeOH、DME和烃,或用于回收H2和/或CO。
Claims (6)
1.通过烃原料的催化蒸汽转化制备富氢和/或富一氧化碳气的方法,其中第一部分原料物流以并联于第二部分原料物流进行自热蒸汽转化,第二部分原料物流在蒸汽转化催化剂存在下与从自热蒸汽转化来的蒸汽转化原料热流出气呈间接热交换和单独地与从蒸汽转化催化剂排出的蒸汽转化热流出气呈间接热交换而进行蒸汽转化,和随后
在流出气给第二部分原料物流中的蒸汽转化反应供给热量之后,使从自热蒸汽转化来的流出气和从蒸汽转化催化剂来的流出气混合。
2.权利要求1的方法,其中蒸汽转化催化剂是以催化剂颗粒的固定床形式。
3.权利要求1的方法,其中蒸汽转化催化剂是以薄膜的形式。
4.反应器系统,包括一台自热转化反应器和一台在反应器入口处并联相接和与自热反应器出口处串联相接的热交换反应器,其中热交换反应器至少装有一根具有内外管双管形式的转化器管,外管装有转化催化剂,内管适用于排出从外管来的蒸汽转化原料的流出气流,外管由与其有一定间隔的套管同轴围绕并适用于通过从自热反应器来的热蒸汽转化流出气流,在套管和外管之间的空间流通的热流出气流与外管中的反应原料呈热传导关系,和
在热交换反应器下游,用以收集给热交换反应器中的蒸汽转化反应供给热量之后、从自热反应器和热交换反应器来的流出气流的收集器。
5.权利要求4的反应器系统,其中转化催化剂是装填在热交换反应器的内外管壁之间的固定床。
6.权利要求4的反应器系统,其中转化催化剂是以薄膜涂敷于热交换反应器外管的内壁和/或内管的外壁上。
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DK199801098A DK173742B1 (da) | 1998-09-01 | 1998-09-01 | Fremgangsmåde og reaktorsystem til fremstilling af syntesegas |
DKPA199801098 | 1998-09-01 |
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CN1124226C true CN1124226C (zh) | 2003-10-15 |
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US (1) | US6224789B1 (zh) |
EP (1) | EP0983963A3 (zh) |
JP (1) | JP2000185906A (zh) |
CN (1) | CN1124226C (zh) |
AU (1) | AU753603B2 (zh) |
DK (1) | DK173742B1 (zh) |
NO (1) | NO994029L (zh) |
NZ (1) | NZ337468A (zh) |
ZA (1) | ZA995562B (zh) |
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- 1999-08-30 US US09/385,724 patent/US6224789B1/en not_active Expired - Lifetime
- 1999-08-31 CN CN99118408A patent/CN1124226C/zh not_active Expired - Lifetime
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EP0983963A2 (en) | 2000-03-08 |
US6224789B1 (en) | 2001-05-01 |
CN1246441A (zh) | 2000-03-08 |
DK199801098A (da) | 2000-03-02 |
NO994029L (no) | 2000-03-04 |
NZ337468A (en) | 2001-01-26 |
NO994029D0 (no) | 1999-08-20 |
EP0983963A3 (en) | 2000-10-04 |
DK173742B1 (da) | 2001-08-27 |
ZA995562B (en) | 2000-10-03 |
JP2000185906A (ja) | 2000-07-04 |
AU4488799A (en) | 2000-03-16 |
AU753603B2 (en) | 2002-10-24 |
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