CN107964426A - 一种二氧化碳零排放的化石燃料制氢方法 - Google Patents
一种二氧化碳零排放的化石燃料制氢方法 Download PDFInfo
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- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
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Abstract
本发明涉及一种二氧化碳零排放的化石燃料制氢方法,本发明的方法将化石燃料和水蒸气气化反应,得到混合气经热回收、三相分离、除尘净化、一次脱硫、二次脱硫碳转换,低温甲醇洗,获得高纯度H2和CO2,CO2由氨气进行吸收制备三嗪醇产品;在获得高纯度H2的同时又获得三嗪醇产品,全程无二氧化碳排放,实现化石燃料清洁化利用;得到了高纯度的H2,几乎不含有任何杂质,热能及物料均能有机的利用起来,能耗低,成本低,操作方便简单,可以大规模生产。
Description
技术领域
本发明涉及一种二氧化碳零排放的化石燃料制氢方法,属于制氢领域。
背景技术
能源是人类生存的基础,煤炭,石油,天然气在过去200多年的大量消耗促进了人类文明的快速进步,但同时也加剧了资源环境的约束,各国均把开发可再生能源作为重大战略计划。氢气不仅可作代替传统能源的洁净能源,同时也是化工,冶金及炼油等行业重要的气体原料。
按照制氢来源进行划分,有化石燃料制氢,生物质制氢及水制氢等。化石燃料制氢包括煤制氢、轻烃蒸汽转化制氢、石脑油制氢,甲醇转化制氢等;生物质制氢主要指微生物在常温常压下将生物质降解得到氢气,根据产氢机理,又可以分为暗发酵、光生物(光发酵和光解水)和光暗发酵耦合制氢3种类型;水制氢按照所消耗能源可分成电解水制氢、光解水制氢、热解水制氢和热化学循环水分解制氢等。
生物制氢具有清洁和不消耗矿物资源等突出优点,但是还处于实验室小型试验的阶段,试验数据亦为短期试验结果,即便瞬时产氢率较高,工业化运行能否获得较高产氢量尚待探讨,无法规模化生产;电解水制氢是制备高纯度氢气的最主要来源,尽管技术成熟、工艺简单,但由于采用直接电解方式,综合考虑发电效率,能量消耗大,成本高。光解水制氢是利用太阳能,未来工业化应用潜力巨大,但是光能利用效率和产氢速率较低,且目前无合适的催化剂。
当前,全球氢气来源主要以化石燃料为主,约占96%,水电解制氢约占3%;化石燃料制氢技术成熟,虽然目前存在投资成本高和碳排放量大等问题,但在其他制氢技术尚不成熟的阶段,可作为过渡性的制氢方式。
化石燃料制氢可分为煤制氢、油品类制氢和天然气重整制氢等。煤制氢是利用气化方法将固态煤转化为气态氢气,可分为煤的气化和煤焦化副产制氢。煤制氢成本较低,按煤价160~560元/t测算,煤制氢的成本仅为0.55~0.83元/m3。而且结合我国煤炭资源分布情况,按照每吨煤制取约900m3氢气计算,全国累计约1900万亿m3,煤制氢的潜力巨大。但是煤制氢存在投资成本高和碳排放量大等问题,若能降低投资成本和控制碳排放,随着氢能应用市场的不断扩大,煤清洁制氢可为发展氢源提供保障。油类制氢的原料主要为石油深加工后的残余物以及常压/减压渣油等重油,重油是炼油过程中的残余物,市场价值不高,用来制氢具有一定的成本优势,随着石油的价格不断攀升,重油制氢成本优势逐步消失。天然气制氢技术主要包括水蒸气重整、部分氧化、自热重整、绝热催化裂解等。水蒸气重整工艺较为成熟,在高温高压条件下,甲烷与水蒸气经催化反应和水煤气变换反应最终生成氢气和二氧化碳。天然气部分氧化重整制氢指甲烷与氧气先进行部分氧化反应,再进行水煤气变换反应,最终同样制得氢气和二氧化碳。天然气制氢的问题在于制氢过程成本高,燃料成本占生产成本的52%~68%;过程中会排放大量的二氧化碳,不仅造成能源的浪费,也造成二氧化碳对全球气候的负面影响。
中国专利文献CN1544309A公开了一种近零排放的固体燃料无氧气化制氢方法。将煤或生物质固体燃料加入到压力循环流化床气化炉中,以水蒸气作为流化气化剂,以CaO吸收CO2产生CaCO3,除尘,净化产生高纯度氢气,CaCO3再送回燃烧炉产生CaO,仍旧释放了CO2。
中国专利文献CN105621357A公开了一种甲烷重整制氢方法,将移动床和固定床耦合起来,简化了装置建设及操作过程、节省了能耗,生产过程中以CaO和MgO为原料制备CO2吸附剂,集中捕集CO2,提高催化剂的使用效率,降低操作成本,混合气体经该装置得到氢气。
上述方法均是通过CaO进行吸附反应体系中的CO2,得到的CaCO3的后续处理没有提及或者再次煅烧仍旧产生CO2。
发明内容
针对现有技术的不足,本发明提供一种二氧化碳零排放的化石燃料制氢方法;该方法将化石燃料和水蒸气进行气化反应,得到混合气经热回收、三相分离、除尘净化、一次脱硫、二次脱硫、碳转换、低温甲醇洗,获得高纯度H2和CO2,CO2由氨气进行吸收制备三嗪醇产品;在获得高纯度H2的同时又获得三嗪醇产品,全程无二氧化碳排放,实现化石燃料清洁化利用。
本发明是通过如下技术方案实现的:
一种二氧化碳零排放的化石燃料制氢方法,包括如下步骤:
(1)化石燃料与水蒸气在压力2~10Mpa、温度1000~1700℃的条件下进行气化反应,获得混合高温燃料气,所述的混合高温燃料气中含H2、CO、CO2、H2S、H2O以及未反应完全的化石燃料气;
(2)混合高温燃料气经余热回收装置进行热回收利用,热回收后的混合高温燃料气进行三相分离,分离得到未反应完全的化石燃料气、水蒸气以及含H2、CO、CO2、H2S、H2O的粗混合气体,未反应完全的化石燃料气与水蒸气返回步骤(1),按步骤(1)的条件再次发生气化反应;
(3)步骤(2)得到的粗混合气体经除尘净化、一次脱硫、二次脱硫,脱除全部硫化物,得初步净化后气体;
(4)初步净化后气体进行碳转换,低温甲醇洗,分别获得高纯度H2和CO2;
(5)将步骤(4)中所获得的CO2由氨气进行吸收制备三嗪醇产品,多余的热气通过回收换热器,进行热回收再利用。
根据本发明,优选的,步骤(1)中,化石燃料与水蒸气的碳水摩尔比为:1:(2~4),气化反应采用气流床气化法进行,气流床气化炉内压力为2~5MPa,温度为1200~1700℃。
进一步优选的,气流床气化法为Shell干粉煤气化法、德士古煤气化法或GSP煤气化法。
进一步优选的,化石燃料与水蒸气的碳水摩尔比为:1:3;气流床气化炉内压力为4.0MPa,温度为1450~1600℃。
根据本发明,优选的,步骤(3)中,除尘净化为布袋式除尘或通过文氏管和纤维除雾器进行除尘。
根据本发明,优选的,步骤(3)中,一次脱硫采用以CaO为基础的湿法脱硫,二次脱硫采用以NH3为基础的干法脱硫。
以CaO为基础的湿法脱硫,以及NH3为基础的干法脱硫均按照常规操作即可。
根据本发明,优选的,步骤(4)中,所述的碳转换为初步净化后气体与水在催化剂存在下反应制得氢气和CO2。
进一步优选的,水与初步净化后气体的摩尔比在1:1~1:5,碳转换温度为150~900℃,压力为2.5~8MPa,催化剂为铁系高温变换催化剂、铜系低温变换催化剂或钴钼系耐硫宽温变换催化剂。
最为优选的,水与初步净化后气体的摩尔比在1:1.4,碳转换温度为300~600℃,压力为2.5-6.5MPa。
根据本发明,优选的,步骤(5)中,CO2由氨气进行吸收制备三嗪醇产品为CO2与NH3按摩尔比为0.5:1~1.2:1的比例混合,在温度200~300℃、压力0~30MPa的条件下,加或不加催化剂,制备三嗪醇产品。
进一步优选的,在催化剂条件下,制备三嗪醇产品,所述催化剂为硫酸铵或氯化铵,催化剂的添加量为CO2和氨气总质量的1-5wt%。
CO2由氨气进行吸收制备三嗪醇产品可参考专利文献CN102633736A进行。
本发明的优点在于,
1、本发明的方法提供了一种制取高纯度氢气的方法,且气化剂仅为水蒸气,化石燃料进行无氧气化,可提高产品气的有效成分含量;将化石燃料和水蒸气气化反应,得到混合气经热回收、三相分离、除尘净化、一次脱硫、二次脱硫碳转换,低温甲醇洗,获得高纯度H2和CO2,CO2由氨气进行吸收制备三嗪醇产品;在获得高纯度H2的同时又获得三嗪醇产品,全程无二氧化碳排放,实现化石燃料清洁化利用。
2、本发明解决了化石燃料制氢过程中碳排放问题,将温室气体二氧化碳转化为稳定的固体产品,对能源结构调整具有重要意义;得到的产品三嗪醇作为一种化工产品,用途广泛,因此可产生明显的经济效益。
3、本发明经经热回收、三相分离、除尘净化、一次脱硫、二次脱硫碳转换,低温甲醇洗,得到了高纯度的H2,几乎不含有任何杂质,热能及物料均能有机的利用起来,能耗低,成本低,操作方便简单,可以大规模生产。
具体实施例
下面结合实施例对本发明做进一步说明,但不限于此。
实施例1
一种二氧化碳零排放的化石燃料制氢方法,步骤如下:
以煤为原料进行二氧化碳零排放的制氢方法。原料煤利用水蒸汽为气化剂,在气流床气化炉,4Mpa的压强和1450~1600℃温度的条件下发生Shell干粉煤气化反应产生水煤气,水煤气经热回收利用,再经三相分离,分离得到未反应完全的化石燃料气、水蒸气以及含H2、CO、CO2、H2S、H2O的粗混合气体,未反应完全的化石燃料气与水蒸气返回气流床气化炉再次发生气化反应;
粗混合气体经布袋式除尘净化后,采用以CaO为基础的湿法脱硫进行一次脱硫,采用以NH3为基础的干法脱硫进行二次脱硫;脱除全部硫化物,再经碳转换,低温甲醇洗。
碳转换为初步净化后气体与水在催化剂存在下反应制得氢气和CO2。水与初步净化后气体的摩尔比在1:1.4,碳转换温度为350℃,压力为6.5MPa,催化剂为铁系高温变换催化剂;由气相色谱法检测氢气纯度可达99.92%。
CO2由NH3进行吸收,CO2与NH3摩尔比为0.5:1~1.2:1,温度在200~300℃之间、压力在0~30MPa之间,可加质量为1-5wt%原料质量的硫酸铵或氯化铵为催化剂,生成三嗪醇产品。多余的热气进行回收再利用,提高整个系统的热效率。
该实施例的反应式为:
C+H2O→CO+H2
CO+H2O→CO2+H2
3CO2+3NH3→C3N3H3O3+3H2O
通过原子守恒,结合上述反应式可以看出,本发明煤的碳能有机的利用起来,碳原子全部转移生成三嗪醇产品,全程无二氧化碳排放,实现化石燃料清洁化利用。
实施例2
一种二氧化碳零排放的化石燃料制氢方法,步骤如下:
以天然气为原料进行二氧化碳零排放的制氢过程类似于煤制氢过程,
天然气经布袋式除尘净化后,采用以CaO为基础的湿法脱硫进行一次脱硫,采用以NH3为基础的干法脱硫进行二次脱硫;脱除全部硫化物,再经碳转换,低温甲醇洗。
碳转换为初步净化后气体与水在催化剂存在下反应制得氢气和CO2。水与初步净化后气体的摩尔比在1:3,碳转换温度为900℃,压力为2.5MPa。由气相色谱法检测氢气纯度可达98%。
CO2由NH3进行吸收,CO2与NH3摩尔比为0.5:1~1.2:1,温度在200~300℃之间、压力在0~30MPa之间,可加质量为1-5wt%原料质量的硫酸铵或氯化铵为催化剂,生成三嗪醇产品。多余的热气进行回收再利用,提高整个系统的热效率。
该实施例的反应式为:
CH4+H2O→CO+3H2
CO+H2O→CO2+H2
3CO2+3NH3→C3N3H3O3+3H2O
通过原子守恒,结合上述反应式可以看出,本发明煤的碳能有机的利用起来,碳原子全部转移生成三嗪醇产品,全程无二氧化碳排放,实现化石燃料清洁化利用。
实施例3
一种二氧化碳零排放的化石燃料制氢方法,步骤如下:
以石脑油为原料进行二氧化碳零排放的制氢方法与以天然气为原料的流程相似。
以重质油为原料可部分进行氢气制取,部分进行其他工业应用。重质油包括各种深度加工所得的渣油,可用部分气化法制得H2、CO和N2等,这里主要采用石脑油。石脑油先经加氢脱硫去除硫化物,再与水蒸气在水碳比为3,4Mpa的压强和650~850℃温度的条件下发生气化反应产生转化气,转化气经热回收利用,再经三相分离,分离得到H2、CO、CO2等粗混合气体。将该粗混合气体通过碳转换,低温甲醇洗,分别获得高纯度H2和CO2,由气相色谱法检测氢气纯度可达98%。CO2由NH3进行吸收,CO2与NH3摩尔比为0.5:1~1.2:1,温度在200~300℃之间、压力在0~30MPa之间,可加质量为1-5wt%原料质量的硫酸铵或氯化铵为催化剂,生成三嗪醇产品。多余的热气进行回收再利用,提高整个系统的热效率。
该实施例的反应式为:
CHn+H2O→CO+H2
CO+H2O→CO2+H2
3CO2+3NH3→C3N3H3O3+3H2O
通过原子守恒,结合上述反应式可以看出,本发明煤的碳能有机的利用起来,碳原子全部转移生成三嗪醇产品,全程无二氧化碳排放,实现化石燃料清洁化利用。
Claims (9)
1.一种二氧化碳零排放的化石燃料制氢方法,包括如下步骤:
(1)化石燃料与水蒸气在压力2~10Mpa、温度1000~1700℃的条件下进行气化反应,获得混合高温燃料气,所述的混合高温燃料气中含H2、CO、CO2、H2S、H2O以及未反应完全的化石燃料气;
(2)混合高温燃料气经余热回收装置进行热回收利用,热回收后的混合高温燃料气进行三相分离,分离得到未反应完全的化石燃料气、水蒸气以及含H2、CO、CO2、H2S、H2O的粗混合气体,未反应完全的化石燃料气与水蒸气返回步骤(1),按步骤(1)的条件再次发生气化反应;
(3)步骤(2)得到的粗混合气体经除尘净化、一次脱硫、二次脱硫,脱除全部硫化物,得初步净化后气体;
(4)初步净化后气体进行碳转换,低温甲醇洗,分别获得高纯度H2和CO2;
(5)将步骤(4)中所获得的CO2由氨气进行吸收制备三嗪醇产品,多余的热气通过回收换热器,进行热回收再利用。
2.根据权利要求1所述的二氧化碳零排放的化石燃料制氢方法,其特征在于,步骤(1)中,化石燃料与水蒸气的碳水摩尔比为:1:(2~4),气化反应采用气流床气化法进行,气流床气化炉内压力为2~5MPa,温度为1200~1700℃。
3.根据权利要求1所述的二氧化碳零排放的化石燃料制氢方法,其特征在于,化石燃料与水蒸气的碳水摩尔比为:1:3;气流床气化炉内压力为4.0MPa,温度为1450~1600℃。
4.根据权利要求1所述的二氧化碳零排放的化石燃料制氢方法,其特征在于,步骤(3)中,除尘净化为布袋式除尘或通过文氏管和纤维除雾器进行除尘。
5.根据权利要求1所述的二氧化碳零排放的化石燃料制氢方法,其特征在于,步骤(3)中,一次脱硫采用以CaO为基础的湿法脱硫,二次脱硫采用以NH3为基础的干法脱硫。
6.根据权利要求1所述的二氧化碳零排放的化石燃料制氢方法,其特征在于,步骤(4)中,所述的碳转换为初步净化后气体与水在催化剂存在下反应制得氢气和CO2。
7.根据权利要求6所述的二氧化碳零排放的化石燃料制氢方法,其特征在于,水与初步净化后气体的摩尔比在1:1~1:5,碳转换温度为150~900℃,压力为2.5~8MPa,催化剂为铁系高温变换催化剂、铜系低温变换催化剂或钴钼系耐硫宽温变换催化剂;最为优选的,水与初步净化后气体的摩尔比在1:1.4,碳转换温度为300~600℃,压力为2.5-6.5MPa。
8.根据权利要求1所述的二氧化碳零排放的化石燃料制氢方法,其特征在于,步骤(5)中,CO2由氨气进行吸收制备三嗪醇产品为CO2与NH3按摩尔比为0.5:1~1.2:1的比例混合,在温度200~300℃、压力0~30MPa的条件下,加或不加催化剂,制备三嗪醇产品。
9.根据权利要求8所述的二氧化碳零排放的化石燃料制氢方法,其特征在于,在催化剂条件下,制备三嗪醇产品,所述催化剂为硫酸铵或氯化铵,催化剂的添加量为CO2和氨气总质量的1-5wt%。
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