CN104692324A - 绝热式天然气催化氧化炉在线烘炉方法 - Google Patents
绝热式天然气催化氧化炉在线烘炉方法 Download PDFInfo
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Abstract
本发明公开了一种绝热式天然气催化氧化炉在线烘炉方法,包括:1)向天然气催化氧化炉中同时充入氧气、天然气和能够降低反应升温速率的控温气体,控制氧气和天然气的摩尔比为0.3~0.6∶1,同时控制控温气体与由氧气和天然气组成的原料气的摩尔比为0.1~7∶1.3~1.6;2)对混合气体进行预热逐步提高温度,直至达氧化反应触发温度时停止预热;3)逐步降低控温气体与原料气的摩尔比例,使反应温度以符合设计烘炉曲线要求的升温速率上升,直至反应温度达到工作温度后停止充入控温气体。本发明解决了烘炉期间温度升高过快的问题,避免了绝热耐火材料因骤热而开裂,保护了天然气催化氧化炉,使其能够平稳地过渡到正常运转的状态。
Description
技术领域
本发明涉及催化氧化炉处理技术,具体地指一种绝热式天然气催化氧化炉在线烘炉方法。
背景技术
随着石油探明储量的降低和可开采资源的逐渐枯竭,以煤炭,天然气及生物质为原料,通过间接转化生产液体车用燃料的技术逐渐得以推广,如:南非的煤制油技术,马来西亚以及卡塔尔的气变油技术,神华的煤制油技术等。随着页岩气开采技术的成功开发和大规模工业应用,天然气产量的提高正在改变着矿物能源结构,给天然气的综合利用带来了广阔的前景。天然气的综合利用是通过先将其转化为中间产品—合成气,然后进一步通过合成技术生产化学品,如:氢气,合成氨,尿素,甲醇,烯烃,石蜡,醋酸及其衍生物,或者合成液体燃料,如:柴油,汽油或航空煤油等高附加值产品。
传统的天然气转化制合成气装置,造气工艺大多采用轻烃水蒸汽转化法或自热重整法,通常采用大型合成氨厂,炼油厂,石油化工厂的制氢装置。以天然气,干气或石脑油为原料生产一氧化碳和氢气的合成气,进而生产液体燃料,其主要原则是尽可能多的生产一氧化碳,但传统轻烃水蒸汽转化法或自热重整法,其出口产品气中的H2/CO组成比例通常在3以上,这意味着该气体需通过分去多余的氢气或通过在原料气中补充二氧化碳的方式调整氢碳比后才能用于合成。
天然气部分氧化是一种全新的由天然气制合成气的工艺路线,根据是否采用催化剂,又分为催化氧化及非催化氧化,其中,在催化氧化中,催化剂床层上甲烷和氧气发生如下反应:
CH4+1/2O2=CO+2H2
该反应在一个绝热反应器内进行,不需要加热,可以副产大量高温高压蒸汽,同时产品气的组成中H2/CO≈2:1,不通过变换或者补碳等手段即可直接用于制取液体燃料。
在绝热式天然气催化氧化炉中进行天然气的催化氧化,绝热式天然气催化氧化炉外部为承压金属壳体,内部为绝热耐火材料,在正常运转时,其温度能够达到800℃,在某些极端的情况下甚至可达1300℃或更高;各种绝热耐火材料都有特定的加热升温曲线,即烘炉曲线,为保证绝热式天然气催化氧化炉中绝热耐火材料的使用性能,需控制炉内气体反应温度,使其以符合绝热耐火材料烘炉曲线要求的速率逐渐缓慢上升。但随着进入绝热式天然气催化氧化炉内原料气体温度的升高,当温度达到催化剂上反应的起燃点时,催化氧化反应会瞬间启动,极速温升,使反应气体的温度瞬间达到800℃甚至更高,使得升温阶段,绝热式天然气催化氧化炉内的温度难以控制,而绝热式天然气催化氧化炉内的绝热耐火材料衬里通常是脆性材料,在遇到这种剧烈温升时很容易产生应力,进而产生裂纹,从而导致氧化炉效率降低甚至失效。
目前,对天然气催化氧化的研究主要集中在催化剂的筛选及制备等方面,如:美国专利US6946114B2报道了用于天然气催化氧化的催化剂的配方及反应性能,而如何有效控制天然气催化氧化炉内温度,从而保护天然气催化氧化炉,使其能够平稳地过渡到正常运转的状态,则尚属技术空白。
发明内容
本发明的目的就是要提供一种绝热式天然气催化氧化炉在线烘炉方法,该方法降低了在线烘炉期间的天然气催化氧化炉温升波动,从而避免了炉内耐火材料衬里产生裂纹,使氧化炉平稳过渡到正常运转状态。
为实现上述目的,本发明采用的技术方案是:一种绝热式天然气催化氧化炉在线烘炉方法,该方法包括以下步骤:
1)向装填了催化剂的天然气催化氧化炉中充入由氧气和天然气组成的原料气、以及能够降低反应升温速率的控温气体,控制所述原料气中氧气和天然气的摩尔比为0.3~0.6∶1,同时控制所述控温气体与所述原料气的摩尔比为0.1~7∶1.3~1.6;
2)对步骤1)中由所述原料气和控温气体混合而成的混合气体进行预热,逐步提高所述混合气体的温度,直至达到氧化反应触发温度时,停止预热;
3)在步骤1)描述的摩尔比范围内,逐步降低所述控温气体与所述原料气的摩尔比例,使所述混合气体的反应温度以符合所述天然气催化氧化炉内绝热耐火材料的设计烘炉曲线要求的升温速率上升,直至反应温度达到工作温度后,停止充入控温气体。
进一步地,所述步骤3)中,在逐步降低所述控温气体与所述原料气的摩尔比例的同时,调节所述原料气中氧气与天然气的摩尔比例,使所述混合气体的反应温度以符合所述天然气催化氧化炉内绝热耐火材料的设计烘炉曲线要求的升温速率上升。
进一步地,所述步骤1)中,所述控温气体为惰性气体、N2、CO2或水蒸汽中一种或多种任意比例的组合。
进一步地,所述步骤2)中,所述氧化反应的触发温度为300~600℃。
进一步地,所述步骤3)中,在逐步降低所述控温气体与所述原料气的摩尔比例的同时,逐步增加所述原料气中氧气与天然气的摩尔比例,使所述混合气体的反应温度以符合所述天然气催化氧化炉内绝热耐火材料的设计烘炉曲线要求的升温速率上升。
进一步地,所述步骤3)中,在所述混合气体的温度从280℃升至750℃的过程中,将所述控温气体与所述原料气的摩尔比从7∶1.3~1.6降低至0~5∶1.3~1.6。
进一步地,所述步骤3)中,在所述混合气体的温度从280℃升至750℃的过程中,将所述控温气体与所述原料气的摩尔比从5.1~7∶1.4~1.6降低至0~5∶1.4~1.6,并同时将所述原料气中氧气与天然气的摩尔比例从0.3~0.4∶1增至0.41~0.6∶1。
与现有技术相比,本发明具有以下优点:
其一,本发明通过在原料气中掺入不具有燃烧或助燃性质的控温气体,利用控温气体降低反应速率并带走一部分热量,在升温阶段通过妥善控制控温气体的摩尔比例来控制反应温度,降低了在线烘炉/起炉期间氧化炉内温度升高波动幅度,避免了触发氧化反应时炉内容易产生的骤热现象,使得反应温度以符合天然气催化氧化炉内绝热耐火材料的烘炉曲线要求的升温速率上升,实现天然气催化氧化炉升温曲线的可控,从而避免了绝热耐火材料因骤热而开裂,保护了天然气催化氧化炉,使其能够平稳地过渡到正常运转的状态。
其二,本发明在原料气中掺入不具有燃烧或助燃性质的控温气体,在升温阶段通过妥善控制控温气体的摩尔比例及同时调节天然气与氧气之间的摩尔比例来控制反应温度,从而提供了一种可控且相对温和的绝热式天然气催化氧化炉的在线烘炉方式,更有效地避免了因产生裂纹而导致氧化炉效率降低甚至失效。
其三,本发明方法能够控制在线烘炉/起炉过程中的升温范围,并降低了绝热式天然气催化氧化炉的积碳风险,使氧化炉能够平稳地过渡到正常运转的状态。
附图说明
图1为一种绝热耐火材料的烘炉曲线。
图2为实施例1中出催化剂床层气体温度随混入N2量的变化图。
图3为实施例2中出催化剂床层气体温度随混入He量的变化图。
图4为实施例3中出催化剂床层气体温度随混入CO2量的变化图。
图5为实施例4中出催化剂床层气体温度随混入N2量的变化图。
图6为实施例5中出催化剂床层气体温度随混入H2O量的变化图。
图7为实施例6中出催化剂床层气体温度随混入Ar量的变化图。
具体实施方式
下面结合附图对本发明作进一步的详细说明,便于更清楚地了解本发明,但它们不对本发明构成限定。
实施例1:
首先,向已经经过干燥并装填了贵金属催化剂的天然气催化氧化炉中送入N2,天然气及氧气,其中,天然气含>99.9%甲烷,天然气流量为1kmol/h;氧气纯度>99.9%,氧气流量为0.6kmol/h;氮气纯度为>99.9%,氮气流量为7kmol/h;然后,对由上述氮气,天然气及氧气混合而成的混合气进行预热,逐步提高混合气温度,直至加热至300℃触发催化氧化反应后,停止预热并逐步减小混入的氮气流量,直至氮气流量降至0,使得反应温度以符合天然气催化氧化炉内绝热耐火材料的烘炉曲线要求的升温速率上升,平稳过渡到1115℃的正常运行工况,天然气催化氧化炉内绝热耐火材料的烘炉曲线如图1所示。
在烘炉阶段,随着N2流量的降低,其中,当N2流量分别为7,6,5,4,3,2,1,0.1kmol/h时,出催化剂床层的气体温度见图2,从图2可以看出炉内气体温度随着N2流量的降低而平缓升高,无骤热现象;在烘炉过程中的各保温阶段,天然气,氧气及N2的摩尔比例见下表1。
实施例2:
首先,向已经经过干燥并装填了贵金属催化剂的天然气催化氧化炉中送入He,天然气及氧气,其中,天然气含>99.9%甲烷,天然气流量为1kmol/h;氧气纯度为>99.9%,氧气流量为0.3kmol/h;He纯度为>99.9%,He流量为7kmol/h;然后,对由上述He,天然气及氧气混合而成的混合气进行预热,逐步提高混合气温度,直至加热至550℃触发催化氧化反应后,停止预热并逐步减小混入的He流量,直至He流量降至0,使得反应温度以符合天然气催化氧化炉内绝热耐火材料的烘炉曲线要求的升温速率上升,平稳过渡到760℃的正常运行工况,天然气催化氧化炉内绝热耐火材料的烘炉曲线如图1所示。
在烘炉阶段,随着He流量的降低,其中,当He流量分别为7,6,5,4,3,2,1,0.1kmol/h时,出催化剂床层的气体温度见图3,从图3可以看出炉内气体温度随着He流量的降低而平缓升高,无骤热现象;在烘炉过程中的各保温阶段,天然气,氧气及N2的摩尔比例见下表1。
实施例3:
首先,向已经经过干燥并装填了贵金属催化剂的天然气催化氧化炉中送入CO2,天然气及氧气,其中,天然气含>99.9%甲烷,天然气流量为1kmol/h;氧气纯度为>99.9%,氧气流量为0.4kmol/h;CO2纯度为>99.9%,CO2流量为7kmol/h;然后,对由上述CO2,天然气及氧气混合而成的混合气进行预热,逐步提高混合气温度,直至加热至600℃触发催化氧化反应后,停止预热并逐步减小混入的CO2流量,直至CO2流量降至0,使得反应温度以符合天然气催化氧化炉内绝热耐火材料的烘炉曲线要求的升温速率上升,平稳过渡到760℃的正常运行工况,天然气催化氧化炉内绝热耐火材料的烘炉曲线如图1所示。
在烘炉阶段,随着CO2流量的降低,其中,当CO2流量分别为7,6,5,4,3,2,1,0.1kmol/h时,出催化剂床层的气体温度见图4,从图4可以看出炉内气体温度随着CO2流量的降低而平缓升高,无骤热现象;在烘炉过程中的各保温阶段,天然气,氧气及CO2的摩尔比例见下表1。
实施例4:
首先,向已经经过干燥并装填了贵金属催化剂的天然气催化氧化炉中送入N2,天然气及氧气,其中,天然气含>99.9%甲烷,天然气流量为1kmol/h;氧气纯度为>99.9%,氧气流量为0.3kmol/h;N2纯度为>99.9%,N2流量为7kmol/h;然后,对由上述N2,天然气及氧气混合而成的混合气进行预热,逐步提高混合气温度,直至加热至300℃触发催化氧化反应后停止预热,逐步减小混入的N2流量的同时逐步调整天然气与氧气的摩尔比例,使得反应温度以符合天然气催化氧化炉内绝热耐火材料的烘炉曲线要求的升温速率上升,平稳过渡到1115℃的正常运行工况,此时,N2流量降至0,天然气和氧气比例达到1:0.6,天然气催化氧化炉内绝热耐火材料的烘炉曲线如图1所示。
在烘炉阶段,随着N2流量的降低及氧气流量的增加,其中,当N2流量分别为7,6,5,4,3,2,1,0.1kmol/h,氧气流量分别为0.3,0.4,0.5,0.6kmol/h时,出催化剂床层的气体温度见图5,从图5可以看出炉内气体温度随着N2流量的降低及氧气流量的增加而平缓升高,无骤热现象;在烘炉过程中的各保温阶段,天然气,氧气及N2的摩尔比例见下表1。
实施例5:
首先,向已经经过干燥并装填了贵金属催化剂的天然气催化氧化炉中送入水蒸汽,天然气及氧气,其中,天然气含>99.9%甲烷,天然气流量为1kmol/h;氧气纯度为>99.9%,氧气流量为0.3kmol/h;水蒸汽纯度>99.9%,水蒸汽流量为7kmol/h;然后,对由上述水蒸汽,天然气及氧气混合而成的混合气进行预热,逐步提高混合气温度,直至加热至600℃触发催化氧化反应后停止预热,逐步减小混入的水蒸汽流量的同时调整天然气与氧气的摩尔比例,即:逐步增加氧气的摩尔比例,使得反应温度以符合天然气催化氧化炉内绝热耐火材料的烘炉曲线要求的升温速率上升,平稳过渡到1342℃的正常运行工况,此时,水蒸汽流量降至0,天然气和氧气比例达到1:0.6,天然气催化氧化炉内绝热耐火材料的烘炉曲线如图1所示。
在烘炉阶段,随着水蒸汽流量的降低及氧气流量的增加,其中,当水蒸汽流量分别为7,6,5,4,3,2,1,0.1kmol/h,氧气流量分别为0.3,0.4,0.5,0.6kmol/h时,出催化剂床层的气体温度见图6,从图6可以看出炉内气体温度随着水蒸汽流量的降低及氧气流量的增加而平缓升高,无骤热现象;在烘炉过程中的各保温阶段,天然气,氧气及水蒸汽的摩尔比例见下表1。
实施例6:
首先,向已经经过干燥并装填了贵金属催化剂的天然气催化氧化炉中送入Ar,天然气及氧气,其中,天然气含>99.9%甲烷,天然气流量为1kmol/h;氧气纯度为>99.9%,氧气流量为0.3kmol/h;Ar纯度为>99.9%,Ar流量为7kmol/h;然后,对由上述Ar,天然气及氧气混合而成的混合气进行预热,逐步提高混合气温度,直至加热至300℃触发催化氧化反应后停止预热,逐步减小混入的Ar流量的同时调整天然气与氧气的摩尔比例,即:逐步增加氧气的摩尔比例,使得反应温度以符合天然气催化氧化炉内绝热耐火材料的烘炉曲线要求的升温速率上升,平稳过渡到1115℃的正常运行工况,此时,Ar流量降至0,天然气和氧气比例达到1:0.6,天然气催化氧化炉内绝热耐火材料的烘炉曲线如图1所示。
在烘炉阶段,随着Ar流量的降低及氧气流量的增加,其中,当Ar流量分别为7,6,5,4,3,2,1,0.1kmol/h,氧气流量分别为0.3,0.4,0.5,0.6kmol/h时,出催化剂床层的气体温度见图7,从图7可以看出炉内气体温度随着Ar流量的降低及氧气流量的增加而平缓升高,无骤热现象;在烘炉过程中的各保温阶段,天然气,氧气及Ar的摩尔比例见下表1。
表1
Claims (8)
1.一种绝热式天然气催化氧化炉在线烘炉方法,其特征在于:该方法包括以下步骤:
1)向装填了催化剂的天然气催化氧化炉中充入由氧气和天然气组成的原料气、以及能够降低反应升温速率的控温气体,控制所述原料气中氧气和天然气的摩尔比为0.3~0.6∶1,同时控制所述控温气体与所述原料气的摩尔比为0.1~7∶1.3~1.6;
2)对步骤1)中由所述原料气和控温气体混合而成的混合气体进行预热,逐步提高所述混合气体的温度,直至达到氧化反应触发温度时,停止预热;
3)在步骤1)描述的摩尔比范围内,逐步降低所述控温气体与所述原料气的摩尔比例,使所述混合气体的反应温度以符合所述天然气催化氧化炉内绝热耐火材料的设计烘炉曲线要求的升温速率上升,直至反应温度达到工作温度后,停止充入控温气体。
2.根据权利要求1所述的绝热式天然气催化氧化炉在线烘炉方法,其特征在于:所述步骤3)中,在逐步降低所述控温气体与所述原料气的摩尔比例的同时,调节所述原料气中氧气与天然气的摩尔比例,使所述混合气体的反应温度以符合所述天然气催化氧化炉内绝热耐火材料的设计烘炉曲线要求的升温速率上升。
3.根据权利要求1或2所述的绝热式天然气催化氧化炉在线烘炉方法,其特征在于:所述步骤1)中,所述控温气体为惰性气体、N2、CO2或水蒸汽中一种或多种任意比例的组合。
4.根据权利要求1或2所述的绝热式天然气催化氧化炉在线烘炉方法,其特征在于:所述步骤2)中,所述氧化反应的触发温度为300~600℃。
5.根据权利要求1或2所述的绝热式天然气催化氧化炉在线烘炉方法,其特征在于:所述步骤3)中,在逐步降低所述控温气体与所述原料气的摩尔比例的同时,逐步增加所述原料气中氧气与天然气的摩尔比例,使所述混合气体的反应温度以符合所述天然气催化氧化炉内绝热耐火材料的设计烘炉曲线要求的升温速率上升。
6.根据权利要求1或2所述的绝热式天然气催化氧化炉在线烘炉方法,其特征在于:所述步骤3)中,在所述混合气体的温度从280℃升至750℃的过程中,将所述控温气体与所述原料气的摩尔比从7∶1.3~1.6降低至0~5∶1.3~1.6。
7.根据权利要求1或2所述的绝热式天然气催化氧化炉在线烘炉方法,其特征在于:所述步骤3)中,在所述混合气体的温度从280℃升至750℃的过程中,将所述控温气体与所述原料气的摩尔比从5.1~7∶1.4~1.6降低至0~5∶1.4~1.6,并同时将所述原料气中氧气与天然气的摩尔比例从0.3~0.4∶1增至0.41~0.6∶1。
8.根据权利要求5所述的绝热式天然气催化氧化炉在线烘炉方法,其特征在于:所述步骤3)中,在所述混合气体的温度从280℃升至750℃的过程中,将所述控温气体与所述原料气的摩尔比从5.1~7∶1.4~1.6降低至0~5∶1.4~1.6,并同时将所述原料气中氧气与天然气的摩尔比例从0.3~0.4∶1增至0.41~0.6∶1。
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JP2003073106A (ja) * | 2001-09-04 | 2003-03-12 | Exxonmobil Research & Engineering Co | 着火系が改善された接触部分酸化 |
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EP1701909A1 (en) * | 2004-01-08 | 2006-09-20 | Syntroleum Corporation | Processes for starting up an autothermal reformer |
JP5374702B2 (ja) * | 2007-03-09 | 2013-12-25 | 国立大学法人横浜国立大学 | 水素生成方法 |
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CN101811666B (zh) * | 2009-02-19 | 2012-03-14 | 中国石油化工股份有限公司 | 天然气催化氧化制取合成气的方法 |
CN102788508B (zh) * | 2011-07-21 | 2014-11-05 | 宁波连通设备制造有限公司 | 用于工业炉模块烘炉方法的烘炉装置 |
CN104534512B (zh) * | 2014-12-26 | 2017-01-18 | 北京神雾环境能源科技集团股份有限公司 | 水冷壁天然气部分氧化转化炉的点火方法 |
CN104692324B (zh) * | 2015-03-25 | 2017-02-01 | 武汉凯迪工程技术研究总院有限公司 | 绝热式天然气催化氧化炉在线烘炉方法 |
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RU2675014C1 (ru) | 2018-12-14 |
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SG11201707658XA (en) | 2017-10-30 |
EP3275835A1 (en) | 2018-01-31 |
JP2018509370A (ja) | 2018-04-05 |
ZA201707040B (en) | 2019-09-25 |
EP3275835A4 (en) | 2018-08-22 |
KR102032040B1 (ko) | 2019-10-14 |
US20180009663A1 (en) | 2018-01-11 |
CN104692324B (zh) | 2017-02-01 |
AU2016236682A1 (en) | 2017-11-09 |
BR112017020417A2 (zh) | 2018-06-05 |
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