CN105257435A - 通过使汽车的二氧化碳转化为燃料以降低机动车源排放 - Google Patents
通过使汽车的二氧化碳转化为燃料以降低机动车源排放 Download PDFInfo
- Publication number
- CN105257435A CN105257435A CN201510616079.5A CN201510616079A CN105257435A CN 105257435 A CN105257435 A CN 105257435A CN 201510616079 A CN201510616079 A CN 201510616079A CN 105257435 A CN105257435 A CN 105257435A
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- China
- Prior art keywords
- carbon dioxide
- tail gas
- reaction
- heat exchanger
- catalytic reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000000446 fuel Substances 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 39
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 31
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 29
- 230000009467 reduction Effects 0.000 title description 2
- 239000007789 gas Substances 0.000 claims abstract description 79
- 230000003197 catalytic effect Effects 0.000 claims abstract description 71
- 239000012528 membrane Substances 0.000 claims abstract description 26
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 25
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 25
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 25
- 238000002485 combustion reaction Methods 0.000 claims abstract description 22
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 241000549556 Nanos Species 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 150000001721 carbon Chemical class 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 239000013589 supplement Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 8
- 239000000376 reactant Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- 230000001131 transforming effect Effects 0.000 description 5
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052572 stoneware Inorganic materials 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
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Abstract
本发明涉及通过将尾气转化为烃类燃料来降低机动车排放物的装置和方法。所述装置和方法弥补了常规排放控制技术,进一步降低了机动车排放有害物质。所述装置包括:换热器,其从为机动车提供动力的内燃机的尾气中提取热能;膜分离器,其从尾气中分离出水和二氧化碳;以及催化反应器,其容纳有纳米催化剂。所述催化反应器接收来自膜分离器的水和二氧化碳,容纳有水和二氧化碳的反应以产生烃类燃料,并且该反应由纳米催化剂催化,并且来自换热器的热能促进了该反应。催化反应器容纳在换热器本体内从而有利于热能的转移。
Description
本申请是申请号为201280052381.7、申请日为2012年10月24日、发明名称为“通过使汽车的二氧化碳转化为燃料以降低机动车源排放”的专利申请的分案申请。
技术领域
本发明涉及通过将二氧化碳转化为烃类燃料以降低机动车排放的方法。更具体而言,本发明的实施方案利用车载换热器和催化转化器将机动车尾气转化为用于机动车内燃机的烃类燃料。
背景技术
几十年来,汽车工业已经认识到了机动车排放物对公共健康和环境的危害。同时众所周知的是,减少机动车排放物的常规方法是低效的。通常,可通过提高发动机效率和/或在燃烧后净化排放物从而减少机动车排放物。例如,可使用二次空气喷射、尾气循环和/或催化转化来净化汽车尾气。
通常,催化转化器包括用于将有毒排放物转化为无毒物质的金属催化剂(例如,铂、钯、铑)。经转化的有毒排放物可包括一氧化碳、氮氧化物和未燃烃。例如,一氧化碳可被氧化并转化为二氧化碳,其中催化剂促进了这种氧化。
催化转化器的应用无法解决与减少机动车排放物相关的所有问题。例如,催化转化器不能减少烃类燃料的燃烧量。此外,催化转化所产生的二氧化碳是造成全球变暖的温室气体。
因此,人们希望获得减少机动车排放物的改进方法。优选地,期望存在能将排放物转化为可用燃料的方法。此外,期望获得也能减少二氧化碳排放量的方法。
发明内容
在一个实施方案中,降低机动车源排放物的装置包括:换热器,其从内燃机的尾气中提取热能,其中内燃机为机动车提供动力;膜分离器,其从尾气中分离出水和二氧化碳;以及具有纳米催化剂的催化反应器,该催化反应器容纳有水和二氧化碳的反应以产生烃类燃料,该反应由纳米催化剂催化。在一个实施方案中,催化反应器接收来自所述膜分离器的水和二氧化碳,并利用来自换热器的热能以促进水和二氧化碳的反应。
在一个实施方案中,所述纳米催化剂为多金属纳米催化剂,其包含钌、锰和镍中的至少一种。在另一个实施方案中,所述纳米催化剂含有约2%至3%的钌、约20%至30%的镍和约15%至20%的锰。在又一个实施方案中,所述纳米催化剂含有约2%的钌、约20%的镍和约15%的锰。
在一个实施方案中,所述膜分离器包括:选择性膜层,其为二氧化硅类膜层、碳类膜层或沸石膜层;以及载体层,其为陶瓷载体、金属载体或氧化铝载体。
在一个实施方案中,催化反应器被所述换热器围绕,使得热能流向催化反应器中保持有纳米催化剂的部分。在一个实施方案中,催化反应器包括用于保持所述纳米催化剂的复合管(multipletube),所述复合管提供了更大的表面积以接收来自换热器的热能。
在一个实施方案中,所述烃类燃料包含乙醇和丙炔。
附图说明
参照下面的说明书、权利要求书和附图,本发明的这些以及其他特征、方面和优点将会变得更容易理解。但是需要注意的是,附图仅示出了本发明的若干实施方案,因此不能认为附图是对本发明范围的限制,本发明的范围还承认其他等效的实施方案。
图1示出了根据本发明的一个或多个实施方案的装置。
图2示出了根据本发明的一个或多个实施方案的流程图。
图3示出了根据本发明的一个或多个实施方案的装置的例子。
图4示出了根据本发明的一个或多个实施方案的换热器和催化反应器。
图5示出了根据本发明的一个或多个实施方案的换热器。
发明详述
虽然将会结合若干实施方案对本发明进行说明,但是应当理解的是,并不旨在将本发明限于那些实施方案。相反,本发明旨在包括涵盖可以包括在由附加的权利要求书所限定的本发明的精神和范围内的所有可供选择的方案、变型和等价形式。
在一个实施方案中,减少机动车排放物的装置包括:换热器,其用于从内燃机的尾气中提取热能,该内燃机为推动机提供动力;膜分离器,其用于从尾气中分离出水和二氧化碳;以及含有纳米催化剂的催化反应器,该催化反应器中容纳有水和二氧化碳的反应以产生烃类燃料。此外,由换热器提取的热能促进了水和二氧化碳的反应。
如图1所示,装置100包括集成的换热器102A和催化反应器102B、催化转化器104、蛇管式换热器106、膜分离器108和排气装置110整体。在一个实施方案中,如下面参照图3所述,将装置100安装在机动车的排放系统中(例如,安装在机动车的底盘上)。
在一个实施方案中,换热器102A和催化反应器102B被集成在一起,使得换热器102A中从尾气提取的热能可被用于促进催化反应器102B中的反应。换热器102A接收来自内燃机的尾气。随着尾气通过换热器102A,从尾气中提取热能,使得尾气在进入催化转化器104之前冷却下来。换热器102A能够(1)从发动机中回收废热并将其用于催化反应器102B,以及(2)使尾气在进入装置100的其它部分之前被冷却。例如,膜分离器108可以包括这样的膜,该膜在相对高压和低于离开内燃机时的尾气温度的温度下工作。
在一些实施方案中,催化反应器102B包括催化体系、光催化体系、电催化体系或是它们适宜的组合。此外,催化反应器102B可以包括固定流化床和催化膜。催化剂可以为担载型纳米结构催化剂,其包括氧化铝、二氧化硅和粘土作为载体,以及如下所述的活性单金属、双金属和三金属材料作为活性成分。
在一个实施方案中,催化反应器102B中包括将CO2和H2O转化为烃类燃料的反应。例如,所述反应可以为产生醇的通用反应,例如:nCO2+(n+1)H2O→CnH2n+1OH+(3n/2)O2,其中n=1、2、3、4、5、6等(例如,当n=1时,那么产物为CH3OH(甲醇),当n=2时,那么产物为C2H5OH(乙醇)等)。在另一个例子中,所述反应的目标是产生烷烃,例如:2nH2O+nCO2→CnH2n+2+2nO2,其中n=1、2、3、4、5、6等。在又一个实施方案中,如下述反应所示,该反应可以随着氧气的释放而产生甲烷(CH4)或混合产物:
●在673K和大气压力下产生乙醇、丙炔和氧气的催化剂促进的反应—5CO2+5H2O→C2H5OH+H3C-C≡CH+7O2
●产生甲醇、乙醇、氧气和丙炔的催化剂促进的反应—6CO2+7H2O→CH3OH+C2H5OH+17/2O2+H3C-C≡CH
在该例子中,可以设计催化剂和反应温度以将某些产物(例如,乙醇)的产量最大化。此外,催化反应器102B所用的纳米催化剂可为包含钌、锰和/或镍的金属纳米催化剂。具体而言,金属纳米催化剂含有约2%至3%的钌、约20%至30%的镍和约15%至20%的锰(例如,2%的钌、20%的镍和15%的锰)。当H2O(蒸汽)和CO2在纳米催化剂的表面分解产并生氧气和氢气时,该反应可由催化剂促进。在该阶段,氢气和氧气可以与碳反应以生成烃类燃料。在一些情况下,由反应得到的新生成的氧可以产生额外的能量,从而降低了对外部热能的需求。
在HussainS.T.等人的NanoCatalystforCO2ConversiontoHydrocarbons,JournalofNanoSystems&Technology,Oct.31,2009中描述了示例性纳米催化剂。在该文章中,所述示例性纳米催化剂按照如下方式制备:
●在去离子H2O中制备含有三氯化钌(0.103g)、四水合硝酸锰(2.285g)和六水合硝酸镍(2.47g)(分析试剂级)的溶液,并用稀盐酸进行酸化以抑制氢氧化物的沉淀。
●然后在蒸发池中将部分浆料(10cm3)加至二氧化钛催化剂载体(3.95g)(350m2g-1),其中对该混合物进行磁力搅拌20分钟并在395K的温度下干燥过夜。
●然后在空气中于600℃的温度下,将制得的催化剂样品煅烧6小时。
基于典型的运转循环(例如,USO6运转循环),根据机动车的速度,尾气排放可为6.5克/秒至200克/秒。在这种情况下,运转循环中的最大速度为80mph左右,其可用于计算用于商业目的的催化剂的量。在实验室测试中,所用催化剂的量为0.5克,其中尾气通过反应器的相应空间速度为6000hr-1至7200hr-1。相比较而言,通过机动车的尾气的质量流率可以为6.5克/秒至200克/秒。在一些实施方案中,基于实验室数量和典型的运转循环,催化反应器102B中使用的催化剂的总量为约120克。在这种情况下,反应器中的转化水平取决于尾气质量流率(即,反应器中的转化率随着尾气质量流率的降低而升高)。
在一个实施方案中,催化转化器104净化来自机动车尾气的有毒物质。具体而言,催化转化器104可以包括用于(1)氧化一氧化碳以生成CO2的金属催化剂、以及用于(2)氧化未燃烃以生成H2O和CO2的金属催化剂。催化转化器104中的反应提高了尾气在通过蛇管式换热器106之前的温度。
在一个实施方案中,在将尾气供给至膜分离器108之前,蛇管式换热器106将尾气的温度降低。蛇管式换热器106可将尾气的热能转移至朝向催化反应器102B行进的反应物。
在一个实施方案中,膜分离器108从由蛇管式换热器106处接收到的尾气中的其他气体中分离出CO2和H2O。膜分离器108可以包括各种膜,其中根据操作条件(如温度)的不同,CO2和H2O被分离为渗透物或截留物质。分离出的CO2和H2O流向催化反应器102B,并且其他气体流向尾气110。然后排气装置110将其他气体排出机动车。
参照图2,示出了将尾气转化为烃类燃料的示例性流程图。在202中,离开机动车发动机的尾气以约850℃的温度进入双管式换热器102A(即,尾气包含由机动车发动机燃烧产生的热能)。在203排出尾气之前,在尾气离开双管式换热器102A并进入203之前,双管式换热器102A从尾气中提取热能。在进入催化转化器104之前,尾气以大约350℃至500℃的温度离开双管式换热器102A。在催化转化器104中,发生反应从而将未燃烧的气态组分转化为N2、CO2、H2O等。在204中,经转化的气体以大约500℃-600℃的温度离开催化转化器106。
然后,经转化的气体通过蛇管式换热器106,从而进一步将热传递给流向催化反应器102B的反应物。在206中,经转化的气体以大约200℃-300℃的温度进入膜分离器108。在膜分离器108中,CO2和H2O从经转化的气体中分离出来。在210中,经分离的CO2和H2O通过蛇管式换热器106,从而将CO2和H2O的温度提高至约500℃。在110中,剩余的气体离开膜分离器108,并以尾气的形式从机动车中排出。在212中,经加热的CO2和H2O流入催化反应器102B。在催化反应器102B中,纳米催化剂促进了将CO2和H2O转化为烃类燃料的反应。在214中,烃类燃料再循环至汽车发动机216中(例如,烃类燃料可以流至燃料管路,化油器或燃料箱),从而减少机动车中的二氧化碳排放。
图2的工艺流程布置(processflowarrangement)将尾气冷却,使得在膜分离器108中可从尾气中分离出低温的CO2和H2O。同时,通过来自双管式换热器102A和蛇管式换热器106的热转移,从而提高了分离后流向催化反应器102B的CO2和H2O的温度。在一些实施方案中,这种工艺流程布置利用了尾气的废热,从而可在没有外部能量的条件下进行反应。如下文中参照图3所述,这种工艺流程布置可沿着尾气管安装在机动车的底盘上。
参照图3,示出了安装在机动车底盘302上的一个示例性装置。机动车的排气总管(exhaustheadpipe)306接收来自内燃机(未示出)的尾气。集成的换热器102A和催化反应器102B被安装至排气总管306。在本例中,排气总管306与集成的换热器102A和催化反应器102B位于该机动车的发动机部分304下方(即,位于机动车的内燃机下方)。排气总管306的尾气通过换热器102A输送至催化转化器104。
邻近发动机部分304的是隔热罩306,当尾气通过该示例性装置时,隔热罩306用于保护机动车免受尾气热量的影响。在这个例子中,隔热罩306包括催化转化器104、蛇管式换热器106、膜分离器108和排气装置110,这些部件分别与上文中参照图1和图2所描述的相应部件大致类似。如图3所示,来自膜分离器108的渗透物210(即,CO2和H2O)被输送至蛇管式换热器106,其将来自于尾气的热能转移至渗透物210。经加热的反应物212随后穿过催化转化器104并到达催化反应器102B。随着经过加热的反应物流向催化反应器102B并在其间流动,可由催化转化器104和换热器102A向经加热的反应物212传递其他热能。催化反应器102B将经加热的反应物212转化为烃类燃料214,然后将其用作机动车的再循环燃料。
参见图4,示出了集成的换热器和催化反应器102A、102B实例。如上所述,集成的换热器和催化反应器102A、102B可以安装在位于机动车底盘上的内燃机和催化转化器之间。尾气202通常以大约800℃至900℃的温度离开发动机,并在离开集成的换热器和催化反应器102A、102B的外管402之前快速冷却至约500℃至600℃。集成的换热器和催化反应器102A、102B位于这样的位置,该位置使得能从尾气202中回收废热并补充在集成的换热器和催化反应器102A、102B的内管404中发生的吸热反应的热需求。
在该实例中,集成的换热器和催化反应器102A、102B为标准的双管式换热器,其中内管404容纳用于反应的催化剂406,并且外管402提供尾气的通道。在另一个实例中,集成的换热器和催化反应器102A、102B可以是壳管式换热器,其包括具有复合管的内壳,该复合管中容纳有催化剂406,其中该复合管可连接至双管式换热器的两端的管板。该复合管提供更大的表面积以用于热传递。在任一个实例中,外管402均可以经过适当的绝热处理,以保存热量并促进传热。
参照图5,示出了膜分离器108的实例。膜分离器108包括膜502,其用于从由催化转化器206处接收的尾气中分离出渗透物210(CO2和H2O)。在一些实施方案中,膜502可以具有中空纤维结构。在这种情况下,膜502包括涂布在稳定载体(例如,陶瓷中空纤维等)上的选择性膜层(未示出)。在其它实施方案中,膜502可具有管状结构。在这种情况下,选择性膜层被涂覆在管式多孔载体(例如,多孔氧化铝管、陶瓷管、多孔金属管等)上。任选地,吹扫气体(未示出)可以注入到膜分离器108中,以有利于收集渗透物210。下面的表I示出了在膜分离器108中可以使用的膜实例。
表I:膜分离器108中可以使用的示例性膜。
通过下列实施例示出了本发明,这些实施例仅用于示例的目的,并且这些实施例并非旨在限制本发明的范围,本发明的范围是通过附加权利要求书来限定的。
实施例-热研究
进行研究以表征:(1)尾气释放的热,(2)尾气的温度,以及(3)排放物组成。另外,进行尾气系统(例如,图1的装置100)的热力学计算。该研究中的具体任务包括:
●估计尾气温度。
●确定发动机尾气的能量在800℃至850℃下运行催化反应器中的利用度。
●确定尾气排放物的组成。
利用发动机系统的气体热力学模拟平台来进行发动机循环的热动力学模拟、输出功率(即,平均指示有效压力(IMEP))、发动机效率、燃油消耗、估计的尾气温度和排放。具体来说,采用基于实验室测试中所用的现代单缸火花点火发动机的输入数据,并利用气体动力学发动机系统模拟平台进行计算,其中所述点火发动机具有入口和排气口几何结构和进气口燃油喷射(PFI)。已针对不同的燃料和燃烧条件对该模型的现有试验数据进行了证实。此外,内燃机入口和排气口几何结构的条件和气体动力学基于实验室发动机,并且实验室发动机中的热传递基于典型的默认值。使用67%的异辛烷和33%的甲苯的混合物(通过液体体积测定)进行模拟,异辛烷/甲苯的转化率(质量分数)为62.2%/37.8%。该燃料混合物通常作为现代汽油的可重现的代表而用于实验室测试。
下表II示出了该模拟结果,其分析表明:
●使用气化的汽油时,平均尾气温度为大约1152K(879℃),其中在排气阀开口处达到最大温度。然而,阀门处和总出口(headexit)处的平均尾气温度分别为约1188K(915℃)和1152K(879℃)。
●可由汽油尾气(最大尾气温度为1123K(850℃))获得的热含量为大约1.559E+0.5kJ/kmol。
●对于汽油模拟,获得的发动机指示效率为40.1%。
表II:
预测(模拟)的发动机性能、尾气温度、燃料消耗和内燃机(ICE)系统的排放(λ=1,rpm=3000)。
上表II示出了尾气总出口的平均尾气温度预计为1152K(879℃)左右,并且已表明机动车排放的尾气温度为约520℃至580℃。因此,尾气穿过尾气系统的热损失为大约300℃至360℃。
下表III示出了在不同的空气流量的影响下,通过燃烧典型的汽油燃料而释放的热量(用kJ/kg表示)。下表IV示出了当燃料在过量空气条件下燃烧时,用摩尔分数表示气体的组成。
表III:对于不同的燃烧空气的值,由燃料混合物释放的热(kJ/kg)。
100%C8H18 | 过量空气系数(λ) |
39583.33 | 0.9 |
47947.06 | 1 |
47837.57 | 1.5 |
表IV:稀薄燃料燃烧(过量空气)时产物的摩尔分数。
燃料中H2百分比 | XCO2 | XH2O | XN2 | XO2 |
0 | 0.08533334 | 0.096 | 0.752 | 0.06666667 |
可从尾气中得到的能量
作为由机动车发动机的废热回收能量的例子,以下是由CleanPowerTechnologies进行测试的结果:
●当柴油发动机以1400rpm运行并产生405bhp时,尾气温度为549℃。
●在0.46Kg/s的质量流速下,尾气的能量值为268kJ/s。
●换热器可以从尾气中回收250℃,这为能量的45%(即,约121kJ/s)。
●然后,系统可以将回收的热能转化为输出为19KW的机械动力,从而提供了约16%的热回收能源效率。
●回收的能量相当于回收大约5%-10%的机动车发动机运转功率。
催化转化器能量回收
通过研究表明,也可从机动车的催化转化器中获得能量。具体而言,催化转化器中发生的化学反应共释放了总计2.8266x106kJ/kmol的热量。
如上文中参照图1至5所述,(1)从由燃料的初始燃烧产生的废热中回收的热能(即,约121kJ/s)以及(2)从催化转化器中回收的热能(即,-2.8266×106kJ/kmol)都可以用于加热提供至催化反应器中的反应物,从而有利于H2O和CO2转化为烃类燃料。
除非本文另有明确指明,否则单数形式的“一个”、“一种”和“所述”包括复数形式的所指对象。“任选”或“可选”是指其后描述的事件或情况可以发生或可以不发生。说明书包括所述事件或情况发生的场合以及所述事件或情况不发生的场合。本文中的范围可能被表述为从约一个特定的值和/或至约另一个特定的值。当表述这样一个范围时,应当理解的是,另一个实施方案是从所述一个特定的值和/或至所述另一个特定的值,以及在所述范围内的所有组合。
虽然结合本发明的具体实施方案对本发明进行了说明,但是,显然的是,根据前述说明,多种替换、修改和变型对于本领域的技术人员来说都是显而易见的。因此,本发明旨在包含落入所附权利要求书的精神和广泛范围内的所有这些替换、修改和变型。本发明可以适当地包括所公开的元素、由所公开的元素组成或基本上由所公开的元素组成,本发明也可以在未披露的元素不存在的情况下实施。
在本申请的上下文中,提到了专利或申请,这些参考文献的全部内容旨在通过引用的方式并入本文,从而更好地描述本发明所属技术领域的状态,除非这些参考文献与本文的描述相矛盾。
Claims (16)
1.一种车载催化装置,所述装置包括:
换热器,其能够从内燃机的尾气中提取热能,所述内燃机为机动车提供动力;
膜分离器,其能够从所述尾气中分离出水和二氧化碳;以及
催化反应器,其容纳在所述换热器本体内,所述催化反应器能够:
接收来自所述膜分离器的水和二氧化碳;
容纳所述水和所述二氧化碳的反应以产生烃类燃料,该反应由纳米催化剂催化;并且
使用来自所述换热器的热能来促进所述水和所述二氧化碳的反应。
2.根据权利要求1所述的装置,其中所述纳米催化剂为包含由钌、锰和镍组成的组中的至少一种金属的多金属纳米催化剂。
3.根据权利要求1所述的装置,其中所述纳米催化剂含有2%至3%的钌、20%至30%的镍和15%至20%的锰。
4.根据权利要求3所述的装置,其中所述纳米催化剂含有2%的钌、20%的镍和15%的锰。
5.根据权利要求1所述的装置,其中所述膜分离器包括:
选择性膜层,选自由二氧化硅类膜层、碳类膜层和沸石膜层组成的组;以及
载体层,其选自由陶瓷载体、金属载体和氧化铝载体组成的组。
6.根据权利要求1所述的装置,其中所述催化反应器被所述换热器围绕,使得所述热能流向所述催化反应器中容纳有所述纳米催化剂的部分。
7.根据权利要求6所述的装置,其中所述催化反应器包括用于容纳所述纳米催化剂的复合管,该复合管提供了更大的表面积以接收来自所述换热器的所述热能。
8.根据权利要求1所述的装置,其中所述烃类燃料包含乙醇和丙炔。
9.根据权利要求8所述的装置,其中所述反应为5CO2+5H2O→C2H5OH+H3C-C≡CH+7O2,其中CO2为二氧化碳,H2O为水,C2H5OH为乙醇,H3C-C≡CH为丙炔,并且O2为氧气。
10.根据权利要求8所述的装置,其中所述烃类燃料还包含甲醇。
11.根据权利要求10所述的装置,其中所述反应为6CO2+7H2O→CH3OH+C2H5OH+8.5O2+H3C-C≡CH,其中CO2为二氧化碳,H2O为水,CH3OH为甲醇,C2H5OH为乙醇,H3C-C≡CH为丙炔,并且O2为氧气。
12.根据权利要求1所述的装置,其还包含催化转化器,所述催化转化器能够氧化所述尾气中的一氧化碳以产生二氧化碳。
13.一种将汽车的二氧化碳转化为烃类燃料的方法,所述方法包括:
从内燃机的尾气中提取热能,所述内燃机为机动车提供动力;
从所述尾气中分离出水和二氧化碳;
通过由纳米催化剂催化的反应将所述水和所述二氧化碳转化为烃类燃料,从所述尾气中提取的热能促进了该反应;以及
将所述烃类燃料供给至所述内燃机以用于燃烧;
其中,所述烃类燃料包含甲醇、乙醇和丙炔,以及
其中,所述反应为6CO2+7H2O→CH3OH+C2H5OH+8.5O2+H3C-C≡CH,其中CO2为二氧化碳,H2O为水,CH3OH为甲醇,C2H5OH为乙醇,H3C-C≡CH为丙炔,并且O2为氧气。
14.根据权利要求13所述的方法,其中所述纳米催化剂为包含由钌、锰和镍组成的组中的至少一种金属的多金属纳米催化剂。
15.根据权利要求13所述的方法,还包括在从所述尾气中分离出所述水和所述二氧化碳之前,将该尾气冷却至200℃至300℃的温度。
16.根据权利要求13所述的方法,其还包括氧化所述尾气中的一氧化碳以产生二氧化碳。
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- 2012-10-24 CN CN201280052381.7A patent/CN103975043B/zh not_active Expired - Fee Related
- 2012-10-24 CN CN201510616079.5A patent/CN105257435B/zh not_active Expired - Fee Related
- 2012-10-24 KR KR1020147013171A patent/KR101867652B1/ko active IP Right Grant
- 2012-10-24 WO PCT/US2012/061603 patent/WO2013063052A1/en active Application Filing
- 2012-10-24 EP EP12783772.2A patent/EP2771431B1/en not_active Not-in-force
- 2012-10-24 US US13/659,305 patent/US8863701B2/en active Active
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2014
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Also Published As
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KR101867652B1 (ko) | 2018-06-14 |
JP6185129B2 (ja) | 2017-08-23 |
CN105257435B (zh) | 2017-11-17 |
US20130098314A1 (en) | 2013-04-25 |
EP2771431A1 (en) | 2014-09-03 |
KR20140096064A (ko) | 2014-08-04 |
JP2017008946A (ja) | 2017-01-12 |
WO2013063052A1 (en) | 2013-05-02 |
US20150000615A1 (en) | 2015-01-01 |
JP6006324B2 (ja) | 2016-10-12 |
JP2015502474A (ja) | 2015-01-22 |
CN103975043B (zh) | 2015-11-25 |
US8863701B2 (en) | 2014-10-21 |
EP2771431B1 (en) | 2017-11-22 |
US9267429B2 (en) | 2016-02-23 |
CN103975043A (zh) | 2014-08-06 |
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