CN1762790B - 氢气生产方法 - Google Patents
氢气生产方法 Download PDFInfo
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- CN1762790B CN1762790B CN2005100976039A CN200510097603A CN1762790B CN 1762790 B CN1762790 B CN 1762790B CN 2005100976039 A CN2005100976039 A CN 2005100976039A CN 200510097603 A CN200510097603 A CN 200510097603A CN 1762790 B CN1762790 B CN 1762790B
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 52
- 239000001257 hydrogen Substances 0.000 title claims abstract description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 45
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000007789 gas Substances 0.000 claims abstract description 77
- 239000000919 ceramic Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 33
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 33
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
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- 229910052742 iron Inorganic materials 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
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- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
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- 239000007788 liquid Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000004227 thermal cracking Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 12
- 239000000047 product Substances 0.000 description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000005336 cracking Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
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- 239000010948 rhodium Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- 238000001291 vacuum drying Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 150000002505 iron Chemical class 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
- 239000003345 natural gas Substances 0.000 description 1
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Abstract
本发明提供了一种生产氢气的方法,该方法通过在足以生成氢气的温度下使含烃气体通过陶瓷整料,并在足以与所述陶瓷整料上的碳反应生成一氧化碳的温度下使含氧气体通过该陶瓷整料。该方法使用一个或多个反应床,以生成氢气之后接着生成一氧化碳的方式循环进行。
Description
本申请要求2004年8月25日提交的美国临时专利申请60/604,285的优先权。
技术领域
将烃转化为含有氢气和一氧化碳的气体在本领域是众所周知的。这些方法的例子包括催化水蒸气转化、自热催化转化、催化部分氧化和非催化部分氧化。这些方法各有优缺点,生成各种比例的氢气和一氧化碳(也称为合成气)。本发明涉及一种通过使用整料(monolith)基催化剂制造氢气或甲烷-氢气混合物的烃裂化方法。本发明还涉及用单机反应器(single unit reactor)生产合成气。
背景技术
部分氧化方法也是广为人知的,并且本领域中具有各种催化部分氧化方法。部分氧化是一个放热反应,其中甲烷之类的烃气体和空气之类的含氧气体在高温下与催化剂接触,以生成含有高浓度氢气和一氧化碳的反应产物。这些方法中所用的催化剂通常为负载在合适载体上的铂或铑之类的贵金属,以及镍之类的其它过渡金属。
部分氧化方法将天然气之类的含烃气体转化成氢气、一氧化碳和二氧化碳与水之类的其它痕量组分。该方法通常是通过将预热的烃和含氧气体注入燃烧室(在燃烧室内,在氧气含量少于完全燃烧所需的化学计量的条件下发生烃的氧化)中进行。该反应在很高的温度(例如高于700℃,经常是高于1000℃),以及高达150个大气压的压力下进行。在一些反应中,也可向燃烧室内注入水蒸气或二氧化碳来改变合成气产物并调节氢气与一氧化碳的比例。
近来,公开了这样的部分氧化方法,其中,在沉积在陶瓷泡沫(整料)载体上的催化剂如金属存在下,在高空速下使烃气体与含氧气体接触。该整料载体充满了铂、钯或铑之类的贵金属,或者镍、钴、铬等其它过渡金属。通常,这些整料载体由氧化铝、氧化锆、氧化镁等固体耐火材料或陶瓷材料制成。在进行这些反应的时候,首先使烃原料气和含氧气体在超过400℃,通常是超过600℃的温度下,以超过每小时100,000的标准气体每小时空速(GHSV)与金属催化剂接触。
然而,这些方法仍然需要进行下游分离以获得分离产物(氢气和/或一氧化碳)。在本发明的烃裂化方法中,氢气和一氧化碳通过循环方式操作,在单个反应器中分别直接制得。
先前的由烃分解制备氢气的方法的缺点在于,在固定床操作中的压降过大,或者循环流化床的操作很复杂。本发明方法提出了这些问题的解决方案,因为所述陶瓷整料具有高孔隙率和大孔径,并且在操作过程中引起的压降可以忽略不计。另外,没有催化剂的移动以及由此带来的磨损、堵塞或者其它与循环流化床相关的问题。此外,先前的方法的注意力集中在产物仅为氢气(M.Poirier和C.Sapundzhiev)或者氢气和碳产物(N.Muradov)。本发明方法能够通过调节含氧气流再生的操作参数,选择性地产生纯CO而不产生CO2,并且CO能连续地收集;从而显著提升产物的价值。
发明内容
本发明提供了一种制备氢气和一氧化碳的方法,它包括以下步骤:
a)在足以生成氢气的温度下使含烃气体通过陶瓷整料;
b)在足以与所述陶瓷整料上的碳反应生成一氧化碳的温度下,使含氧气体通过该陶瓷整料。
本发明的方法宜循环地进行。所述气体的气流可在至少两个反应器之间交替,以获得连续的产物流。在步骤之间,用氮气之类的惰性气体对包含陶瓷整料的反应器进行短暂的吹扫,以避免形成可燃性混合物。
在本发明的其它实施方式中,一氧化碳可作为第二产物收集,或者可送入变换反应器中以制得更多的氢气。
在本发明的另一个实施方式中,可调节再生条件,通过将沉积在催化剂表面上的碳完全氧化来获得二氧化碳一种产物。
在本发明的另一个实施方式中,通过控制气体的加入流速和陶瓷整料的操作温度来或者主要含有甲烷和约20-30体积%氢气的产物气体混合物。
附图说明
图1为用来生产氢气和任选的一氧化碳的双床整料反应器***的示意图。
图2为用来生产氢气的双床***的示意图。
具体实施方式
氢气由本发明的方法按下述制备:首先使甲烷之类的含烃气流通入含有陶瓷整料的反应器中,该陶瓷整料充满了催化剂。烃在约1-30巴的压力下通过该陶瓷整料。
在该方法的第二个步骤中,使含氧气体(例如空气、富氧空气、纯氧或氧气与水蒸气的混合物)通入该反应器,与最初焦结沉积在陶瓷整料上的碳发生反应。调节操作条件,以形成一氧化碳,所述一氧化碳可作为产物收集或直接导入变换气体反应器进一步生产更多的氢气。
在这两个步骤之间,向反应室内通入选自氮气、氩气、氦气或水蒸气的惰性气体以吹扫反应室。所述惰性气体宜为水蒸气。这将在整个方法过程中抑制可燃性混合物的形成,并且水蒸气可通过冷凝从氢气和一氧化碳的产物气体中较简单地分离。该方法的第一个步骤(裂化步骤)是吸热的,而第二个步骤(烧焦)是放热的。第二个步骤中产生的热量将储存在陶瓷整料体内或呈其它形式热质的形式(例如反应器中的化学瓷料),并用于该方法的第一个步骤中。
所述含烃气体可以是任何气态烃或可汽化的液态烃本身,或者与其它含烃气体的混合物。较佳地,所述含烃气体选自乙烷、丙烷、丁烷、苯、或者它们的混合物。
用于生产氢气和一氧化碳的含烃气体的气体流速约为690-1380小时-1,当第二个步骤中使用空气时,该气体流速约为1725-3450小时-1。当使用氧气时,该气体流速约为345-690小时-1。
进行第一个步骤(裂化)时的温度约为700-900℃。第二个步骤在大致相同的温度下进行。
较佳地,含烃气体在大于500℃,更好是大于约500℃的温度下进行。
较佳地,含氧气体在大于约25℃,更好是在大于约100℃的温度下与水蒸气一起加入。
在本发明的另一个实施方式中,以能生成包含甲烷和氢气的混合物的方式控制所述第一个步骤中反应器的操作条件。控制含烃气体的加料流速和反应室的操作温度,从而制得甲烷和氢气的混合物(含有约20-30体积%的氢气)。该混合物可用作汽车发动机或其它内燃机设备的燃料,特别是用来减少氮氧化物(NOx)和其它排放物的生成,并能提高发动机的效率。所述对反应器***的“调节”能够产生含有约20-100体积%的控制量的氢气的产物气体,该产物气体可用于各种工业用途。在850℃和5磅/平方英寸(psig)下进行的研究得到含有35%甲烷和58%氢气的气体混合物。
也可以对再生条件进行调节,使得产物全都是二氧化碳。这同样包括调节反应条件,使得在引入该反应的第二个步骤反应时调节含氧气体(例如空气、富氧空气、纯氧、或者氧气与水蒸气的混合物)的含量。通过引入化学计量或大于化学计量的含氧气体以使得环境富氧,可得到二氧化碳而不是一氧化碳。
本发明所用的金属催化剂由陶瓷整料载体结构构成,该陶瓷整料载体结构由氧化铝基材组成并充满了Fe、Ni、Pd之类的过渡金属或者它们的混合物。本文中使用的“金属催化剂”指的是包括金属和整料载体的整个催化剂结构。该整料载体通常是由单一结构单元形成的陶瓷泡沫状结构,其中,通道以不规则的或规则的模式排列,相邻的通道之间有间隔。所述单一结构单元用来代替常规的微粒状或颗粒状催化剂(它们在本发明的方法中是较为不利的)。所述不规则模式的整料载体的例子包括用于熔化金属的过滤器。规则模式载体的例子包括用于纯化机动车废气和用于各种化学工艺中的整料蜂巢状载体。优选的是具有不规则通道的陶瓷泡沫结构。这两种类型的整料载体都是人们已知的,都可以商业购得。
所述催化剂元件由陶瓷泡沫整料构成,所述陶瓷泡沫整料基本上由氧化铝构成,并含有约0.5-5重量%的过渡金属(较佳的是金属单质铁、镍、钯、或者它们的混合物)。任选地,可使用约2-5重量%的铁本身或其与其它金属的混合物。反应器包括若干陶瓷泡沫圆盘,包括其上充满了催化剂,且剩下的空白部分用来填充空隙空间的那些。空白圆盘可由氧化铝、氧化锆、堇青石、或者它们的混合物制成。充满的金属可与氧化铝一同用作用于裂化过程的催化剂。含有催化剂的圆盘的孔隙率为40-70孔/英寸(ppi),以使催化剂的负载达到最大。空白圆盘具有20-40ppi的较高孔隙率,以保持低的压降。
以下参看附图,图1为用于进行本发明的双床反应器***的示意图。线路1通过阀1A和线路3将含烃气体输送到阀3A。含烃气体继续通过线路7到达第一陶瓷整料床A。含氧气体从线路2经过阀2A和线路4到达阀12A,在含烃气体流动停止之后进入陶瓷整料床A。在该实施方式中,双床***能够连续制得氢气产物,并且在通过线路12通入含烃气体和含氧气体这两个步骤之间,通过线路5和阀2A、线路4和阀12A将氮气之类的惰性气体引入陶瓷整料床A或B内。
含烃气体通过陶瓷整料床A之后,氢气产物将作为产物经线路9和阀9A从线路14流出。此时含氧气体将进入线路12,然后进入陶瓷整料床B,并在那里与陶瓷整料上的碳发生反应生成一氧化碳,生成的一氧化碳流过线路11、阀11A并经线路13离开陶瓷整料床B。还可含有一定量二氧化碳的一氧化碳气流从这里任选地进入变换转化器C,同时水蒸气通过线路15进入。变换转化所得的产物气体是氢气和二氧化碳,它们经线路16离开。
当陶瓷整料床B用作生产反应器时,含烃气体从阀3A进入线路8,然后流入陶瓷整料床B,在那里反应产物氢气作为产物经过线路10、阀9A和线路14流出***。同时,含氧气体将经过线路4、阀12A和线路12进入陶瓷整料床A。在那里它将与陶瓷整料A上的存在的碳发生反应,生成的一氧化碳气体从线路11离开。该一氧化碳中还可能存在一定量的二氧化碳,该混合物将通过阀11A离开,然后经线路13送入变换反应器中。
应当注意的是,如果需要一氧化碳/二氧化碳作为最终产物,可将其从线路13排出而不进入变换反应器中。
图2为与图1中所示结构不同的用于生产氢气的双床方法的示意图。含烃气体将通过线路20进入陶瓷整料床D(它是固定床陶瓷整料)。含烃气体将在该陶瓷整料床内发生反应,生成的氢气作为产物气体通过线路21离开。在这种情况下阀22A和32A是关闭的。含氧气体将经线路27和线路28进入陶瓷整料床E并在那里发生反应,生成的一氧化碳和一些二氧化碳经线路26和线路25流出。
当陶瓷整料床E为生产床时,含烃气体经线路20和线路22通过阀22A,或者经线路24和阀24到达线路26,在那里含烃气体将在陶瓷整料床E内与陶瓷整料发生反应。生成的氢气将作为产物气体经线路28、线路32,通过阀32A,或者经线路30和阀30A以及线路21排出。同时,含氧气体经线路27,然后经线路30和阀30A或者线路32和阀32A进入线路21,在那里含氧气体将进入陶瓷整料床D。所述含氧气体将发生反应,生成的含有一些二氧化碳的一氧化碳气体通过线路20离开陶瓷整料床D,然后经线路22和阀22A或者线路24和阀24A进入线路26,然后从线路25排出。图中未显示,但与本发明一致的是,可将一氧化碳气体导入变换转化器内,并在那里用于生产更多的氢气。
实施例
整料催化剂的制备
具有氧化铝洗涂层(washcoat)且每英寸具有45个孔(ppi)的整料是商业可得的,其长度为3英寸和6英寸,直径1.5英寸。用水浸泡3英寸长的整料,然后真空干燥2小时以记录该整料的重量增加。通过将Fe、Ni和Pd的盐溶解于水中制备铁、镍和钯的溶液,用来在该整料上负载3-5重量%的金属。
对在制得的盐溶液中的浸渍过的整料进行真空干燥之后,将其在800℃的氮气中煅烧过夜,随后在含5%氢气的氮气气氛中还原近似长的时间。应当注意的是,发现该还原时间对试验而言略显不足,这是因为在还原步骤之后该整料上仍残留有一定量的氧化铁。
试验步骤
用于试验本发明方法的试验步骤是两步循环过程。在第一个步骤中,通过压力调节器和一系列阀调节压力和流速,将甲烷通入含有已通过上述方法制备的催化剂的加热炉内。在第二个步骤中,通过压力调节器和阀以逆流方式向加热炉内通入空气,并调节空气流速以更有利于选择性地生成CO。在热裂化步骤(步骤I)和催化再生步骤(步骤II)之间需要以氮气作为吹扫气体来进行短暂的吹扫步骤(本发明人预期也可使用水蒸气)。
所述加热炉在700℃、800℃和900℃的温度下操作。甲烷以很多种空速通过加热炉。试验三种不同的催化剂:3.5%铁、2%镍和2%钯。
使用下式(1)测量甲烷向氢气的转化率,其中P为观测到在离开加热炉的产物气体中氢气的浓度。该试验的结果列于表1a、1b和1c。
表1a.在900℃的产物气体中观测到的最大氢气浓度
空速(h-1) | Fe(3.5%) | Ni(2%) | Pd(2%) |
375 | 89 | 84.5 | 92.3 |
550 | 89 | ||
750 | 89 | 80 | 91.5 |
900 | 88.5 | ||
1100 | 86 | 82 | 90 |
2150 | 87 |
表1b.在800℃的产物气体中观测到的最大氢气浓度
空速(h-1) | Fe(3.5%) | Ni(2%) | Pd(2%) |
375 | 89 | 82 | 87 |
550 | 89 | ||
750 | 88 | 79 | 86 |
900 | |||
1100 | 85 | 75 | 85 |
表1c.在700℃的产物气体中观测到的最大氢气浓度
空速(h-1) | Fe(3.5%) | Ni(2%) | Pd(2%) |
375 | 80 | 76 | 62 |
550 | 75 | ||
750 | 72 | 73 | 63 |
900 | |||
1100 | 68 | 70 | 59 |
应当注意的是,如果X为甲烷向氢气的转化率百分数,并且如果P为表1a、1b和1c中给出的产物气体中观测到的氢气浓度,则可用方程式(1)求出X的大致近似值。
X=P/(200-P) (1)
该试验的结果证明,Fe和Pd催化剂在800℃和900℃下在性能方面优于Ni催化剂。还发现在第一个步骤中,产物气体中一氧化碳的含量通常约为2-10体积%。
按上述进行进一步的试验来确定更高催化剂负载的效果。按上述方法制备浓度高于制备3.5重量%的催化剂所需浓度的铁盐溶液。铁的负载量达到约5重量%。
表2a和2b总结了3.5重量%和5重量%铁整料在产物气体中观测到的最大氢气浓度方面的比较。如上文中使用的,方程式(1)提供了各种情况下对甲烷转化率的估计。
表2a.在900℃下3.5重量%和5重量%Fe整料的比较
3.5%Fe整料 5%Fe整料
空速(H-1) | 产物中的最大%H2 | 最大%CH4裂化 | 产物中的最大%H2 | 最大%CH4裂化 |
375 | 89 | 80.2 | 92.3 | 85.5 |
550 | 89.2 | 80.5 | ||
750 | 89 | 80.2 | 93 | 87 |
900 | 88.5 | 80.0 | ||
1100 | 86 | 75.4 | 92 | 85.2 |
1700 | 88.8 | 80.0 |
表2a.在800℃下3.5重量%和5重量%Fe整料的比较
3.5%Fe整料 5%Fe整料
空速(H-1) | 产物中的最大%H2 | 最大%CH4裂化 | 产物中的最大%H2 | 最大%CH4裂化 |
375 | 89.4 | 80.6 | 90.1 | 82 |
550 | 88.8 | 80.1 | ||
750 | 87.7 | 78.1 | 89.7 | 81.3 |
1100 | 85.0 | 73.9 | ||
1700 | 81.2 | 68.4 |
尽管在整料催化剂上负载更多的Fe促进了甲烷的裂化,但是在900℃下效果最好。
尽管本发明已经参照具体的实施方式进行了描述,但是对本领域的技术人员来说,显而易见的是本发明还有很多其它形式和修改。所附的权利要求书和本发明通常应当解释为包括在本发明的真实精神和范围之内的所有这些明显的形式和修改。
Claims (8)
1.一种生产氢气的热裂化方法,它包括以下步骤:
(a)在700-900℃的温度下使含烃的第一气流通过陶瓷整料承载的催化剂,以形成在所述陶瓷整料承载的催化剂上的碳,其中,所述陶瓷整料承载的催化剂由氧化铝基材组成并充满了选自Fe、Ni、Pd及其组合的过渡金属;
(b)在700-900℃的温度下使含氧的第二气流通过所述陶瓷整料承载的催化剂,以与步骤(a)中形成在所述陶瓷整料承载的催化剂上的碳反应,以产生一氧化碳或二氧化碳。
2.如权利要求1所述的方法,其特征在于,所述含烃的第一气流是气态烃或可汽化的液态烃,或者它们的混合物。
3.如权利要求1所述的方法,其特征在于,在1-30巴的压力和大于300℃的温度下使所述含烃的第一气流通过所述陶瓷整料承载的催化剂。
4.如权利要求1所述的方法,其特征在于,所述方法是循环方法。
5.如权利要求1所述的方法,其特征在于,在步骤(a)和步骤(b)之间用惰性气体对所述陶瓷整料承载的催化剂进行吹扫。
6.如权利要求1所述的方法,其特征在于,将由步骤(b)中的反应产生的热量储存在所述陶瓷整料承载的催化剂中,并用于该方法的步骤(a)中。
7.如权利要求1所述的方法,其特征在于,所述陶瓷整料为陶瓷泡沫状结构。
8.如权利要求1所述的方法,其特征在于,所述陶瓷整料呈圆盘或圆柱的形状。
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KR100599668B1 (ko) * | 2004-08-19 | 2006-07-12 | 한국과학기술연구원 | 연료의 부분 산화 개질 반응용 촉매 성형체 더미, 이를 이용한 연료 개질 장치 및 연료 개질 방법 |
WO2007112491A1 (en) * | 2006-03-31 | 2007-10-11 | The University Of Tasmania | Microreactor |
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Also Published As
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KR20060092856A (ko) | 2006-08-23 |
CN1762790A (zh) | 2006-04-26 |
EP1630129A1 (en) | 2006-03-01 |
CA2512958A1 (en) | 2006-02-25 |
KR101180251B1 (ko) | 2012-09-05 |
CA2512958C (en) | 2014-06-03 |
US7544342B2 (en) | 2009-06-09 |
TW200621629A (en) | 2006-07-01 |
TWI373451B (en) | 2012-10-01 |
US20060045844A1 (en) | 2006-03-02 |
SG120243A1 (en) | 2006-03-28 |
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