CN103820183A - 一种焦炉气直接补二氧化碳制合成天然气的方法 - Google Patents
一种焦炉气直接补二氧化碳制合成天然气的方法 Download PDFInfo
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- CN103820183A CN103820183A CN201410065700.9A CN201410065700A CN103820183A CN 103820183 A CN103820183 A CN 103820183A CN 201410065700 A CN201410065700 A CN 201410065700A CN 103820183 A CN103820183 A CN 103820183A
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- 239000007789 gas Substances 0.000 title claims abstract description 185
- 239000000571 coke Substances 0.000 title claims abstract description 80
- 239000003345 natural gas Substances 0.000 title claims abstract description 40
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound 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O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 title abstract description 7
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 239000001569 carbon dioxide Substances 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 108
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 47
- 230000003009 desulfurizing Effects 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000012528 membrane Substances 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 238000002309 gasification Methods 0.000 claims abstract description 14
- 238000000746 purification Methods 0.000 claims abstract description 7
- 238000007906 compression Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 24
- 235000011089 carbon dioxide Nutrition 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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[C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
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Abstract
本发明提供一种焦炉气直接补二氧化碳制合成天然气的方法,主要工序包含焦炉气压缩、净化、CO2气化、甲烷化和膜分离,焦炉气净化由初脱硫、变温吸附深度净化和精脱硫组成,甲烷化工序为三级甲烷化反应。在甲烷化反应过程中补充CO2,最大限度实现混合气体中CO2和H2的充分利用;按一定比例分配甲烷化合成气进入末级甲烷化反应器之前的反应器以及末级甲烷化反应器之前的甲烷化反应器甲烷化间气体的部分内循环来实现甲烷化反应的反应平衡、反应压力和反应放热的有效控制,并取得了非常满意的技术效果。在提高合成天然气中CH4的产量的同时,降低焦炉煤气合成天然气运行成本。同时实现了温室气体CO2的减排,不仅能产生很好的经济效益,还具有良好的环保效益。
Description
一种焦炉气直接补二氧化碳制合成天然气的方法
技术领域
[0001] 本发明涉及一种合成天然气的制取方法,特别是涉及一种焦炉气直接补二氧化碳制合成天然气的方法。
背景技术
[0002] 焦炉气或焦炉煤气制合成天然气技术(包括SNG、CNG和LNG),也被人们称为焦炉气或焦炉煤气转化合成天然气技术、焦炉气或焦炉煤气制合成天然气技术等。该技术是近年来在焦化行业发展起来的一项焦炉煤气综合利用新技术。目前,国内焦炉气制合成天然气工艺技术主要有“甲烷化工艺”和“分离工艺”两种。其中,甲烷化工艺又可进一步分为“不补碳甲烷化工艺”和“补碳甲烷化工艺”两种类型。由于焦炉气中CH4的体积分数仅有23%~27%,采用物理法来富集CH4,能耗高、经济效益比较差,且副产物H2产量较高,分离工艺复杂。采用不补碳甲烷化工艺生产天然气,H2仍会有剩余,原料不能够得到充分利用;补碳甲烷化工艺通过对原料气进行补碳,充分利用了焦炉煤气中的各种有效成分,从而使原料气全部甲烷化,可使天然气增产约30%,由于甲烷化工艺省略了脱碳工序,有利于后续气体分离和低温液化,因此是一种较为理想的焦炉气转化天然气的途径。
[0003] 公开号为CN 101100622 A的中国发明专利,公开了一种焦炉气合成CH4的方法,提到对精脱硫后的焦炉气进行补碳合成CH4的工艺,该工艺充分利用了焦炉气中的H2,但是由于其补碳量为焦炉气体积的10~15%,受甲烷化反应及反应平衡的限制,补碳量偏高,导致合成气中的CO2并不能反应完全,而且该方法还通过提取CO2加压在返回到甲烷化一段入口,导致产生甲烷化转化率偏低而投资成本反而增加的弊端。
[0004] 公开号为CN 101597527 A的中国发明专利,公开了一种利用焦炉气制取合成天然气的方法,该方法通过向粗脱硫后的焦炉气中补入碳源,使焦炉气气体体积百分比满足(H2-3C0)/C02 ^ 4的化学计量比,然后在Ni系催化剂作用下进行甲烷化反应。但是,该技术的缺点是向焦炉气中补碳,仅仅是为了优化焦炉气中H2、C0、C02的化学计量比,合成气中的CO2仍然得不到充分利用,需要增设深度脱碳工序,然后再将脱出的CO2返回补碳气循环使用,同样导致投资成本增加。
[0005] 此外,公开号为CN 101712897 A的中国发明专利,公开了一种补碳返氢工艺实现焦炉煤气甲烷化合成天然气的方法,该方法提出在二级甲烷化反应器(补碳返氢工段甲烷化反应器)补充CO2以及甲烷化反应后通过膜分离装置分离得到的H2,从而提高了合成气中CO2转化率,增加了产品天然气中CH4的产量,但是该方法需通过初级约为600°C、二级(补碳返氢级)约为500°C,末级约为360°C的三级反应温度均相差较大的甲烷化反应来实现,其温度控制比较困难,因此工艺流程相对复杂,效率不高。
发明内容 [0006] 本发明要解决的技术问题是提供一种焦炉气直接补二氧化碳制合成天然气的方法,通过在甲烷化反应过程中补充CO2,最大限度地实现混合气体中CO2和H2的充分利用,在提高合成天然气中CH4的产量的同时,降低焦炉煤气合成天然气运行成本。
[0007] 为了解决上述技术问题,本发明所采取的技术方案如下:
一种焦炉气直接补二氧化碳制合成天然气的方法,该方法的主要工序包含焦炉气压缩、净化、CO2气化、甲烷化和膜分离,所述焦炉气净化由初脱硫段、变温吸附深度净化段和精脱硫段组成,所述甲烷化工序采用由一段甲烷化反应器10、二段甲烷化反应器12和三段甲烷化反应器14组成的三段甲烷化反应系统,所述三段甲烷化反应系统中的各段甲烷化反应器均采用绝热式反应器,所述甲烷化催化剂采用专用的Ni系甲烷化催化剂,其特征在于:本发明所述方法中,进入一段甲烷化反应器10的焦炉气和二段甲烷化反应器12的焦炉气为从精脱硫段出来的补充CO2后的焦炉气;所述三段甲烷化反应系统的反应平衡、反应压力及反应放热的控制是通过按比例分配进入一段甲烷化反应器10的焦炉气和二段甲烷化反应器12的焦炉气的气体体积,以及一段甲烷化反应后的气体和二段甲烷化反应后的气体之间的部分循环来实现的;该气体之间的部分循环是通过在精脱硫段和二段甲烷化反应器12之间设置一个或多个稀释气混合器9来实现的。
[0008] 一种优选的技术方案是,本发明所述方法中,所述二段甲烷化反应器12采用串联的两级甲烷化反应器。
[0009] 进一步地,通过本发明所述方法中的甲烷化反应的反应平衡、反应压力和反应放热的控制,从精脱硫段出来的补充CO2后的焦炉气进入一段甲烷化反应器10的气体和二段甲烷化反应器12的气体的体积比为1: (I~3),从二段甲烷化反应器12出来的甲烷化后气体进入稀释气混合器9的气体和三段甲烷化反应器14的气体的体积比为1: (I~3)。
[0010] 进一步地,所述焦炉气补碳的来源为低温液态商品CO2,所述低温液态商品CO2经过CO2气化工序转变为具有自压的CO2气体,然后将该处于气态的CO2气体从精脱硫段连续补入甲烷化反应系统,所述三段`甲烷化反应系统中补入的CO2气体的体积为所述焦炉气气体体积的4%~8%。
[0011] 进一步地,所述低温液态商品CO2经过CO2气化工序转变为具有自压的CO2气体是通过水浴式气化器完成的。
[0012] 进一步地,所述方法的三段甲烷化反应系统的热量控制还包括热量移出系统,通过所述热量移除系统可以副产一定量的3.8MPa、450°C的水蒸汽,另一部分具有一定热量的循环热水则补入水浴式气化器,用于CO2气化工序,从而形成甲烷化移热系统热量的梯级利用。
[0013] 通过本发明所述方法的三段甲烷化反应系统的反应平衡、反应压力和反应放热的控制,一段甲烷化反应器10、二段甲烷化反应器12和三段甲烷化反应器14的操作温度均控制在300°C~650°C,反应压力均控制在2.3MPa~2.7MPa。
[0014] 本发明所述的方法中,所述初脱硫段和精脱硫段均采用干法脱硫,其中所述初脱硫段采用Fe2O3脱硫剂或Fe-Mn脱硫剂或ZnO脱硫剂,所述精脱硫段采用ZnO脱硫剂。
[0015] 本发明所述的方法中,所述膜分离工序包括由压缩机16和气液分离器17顺次连接组成的气液分离段和由膜分离装置18组成的膜分离段,该气液分离段设置于所述膜分离工序的膜分离段之前,本发明所述方法的三段甲烷化反应系统在甲烷化反应过程中所产生的H2O通过该气液分离段除去。
[0016] 本发明所述的方法中,经过膜分离工序后产生的富余H2返回到变温吸附深度净化工序循环使用。
[0017] 与现有技术焦炉气制取或合成天然气的方法相比,本发明在多段甲烷化反应系统中,通过按比例分配甲烷化合成气进入末段甲烷化反应器之前的反应器以及末段甲烷化反应器之前的甲烷化反应器间甲烷化气体的部分内循环来实现甲烷化反应系统的反应平衡、反应压力和反应放热的有效控制,并且取得了非常满意的技术效果。
[0018] 本发明通过在甲烷化反应过程中补充CO2,最大限度地实现混合气体中0)2和&的充分利用,在提高合成天然气中CH4的产量的同时,降低焦炉煤气合成天然气运行成本。同时,本发明通过焦炉煤气补充二氧化碳制合成天然气实现温室气体CO2的减排,不仅能产生很好的经济效益,而且还具有良好的环保效益。
[0019] 此外,本发明通过在三段甲烷化反应系统中设置热量移除系统,不仅起到有效地辅助控制本发明三段甲烷化反应系统的操作温度,而且同时副产蒸汽,在满足自身甲烷化反应器利用蒸汽的同时,又能通过外供蒸汽产生提升本发明整体的经济效益。
附图说明
[0020] 图1是本发明方法工艺流程示意图;
图2是本发明装置工艺流程示意图。
[0021] 图中,1-压缩机;2_初脱硫器;3_TSA净化器;4_精脱硫器;5_C02储槽;6_ CO2气化器;7-止回阀i ;8_止回阀ii ;9_稀释气混合器;10-—段甲烷化反应器;11-换热装置I ;12_ 二段甲烷化反应器;13-换热装置II ; 14-三段甲烷化反应器;15-换热装置III;16-压缩机;17-气液分离器;18-膜分离装置。`具体实施方式
[0022] 以下结合附图对本发明的目的、原理和特征进行最佳实施例的具体描述。
[0023] 本发明的目的是充分利用焦炉煤气中的氢气,以焦炉煤气为原料气通过补充一定量的CO2气体配制成合适碳氢比例的合成气,然后再通过甲烷化、膜分离制SNG,同时副产蒸汽。
[0024] 图1为本发明方法工艺流程示意图。由图1可知,本发明的主要工序包含焦炉煤气压缩工序、焦炉煤气净化工序、甲烷化工序和CO2气化工序。
[0025] ( I)焦炉煤气压缩工序
本发明方法所采用的原料气是来自太原某公司焦化厂生产的焦炉煤气,该焦炉煤气在该公司焦化厂已经过初步处理,但是根据该公司焦化厂所提供的焦炉煤气的组成及杂质情况数据,本发明方法在进行焦炉气合成天然气之前,仍需经过脱苯、脱萘、粗脱硫及脱焦油处理,以及后续的深度净化处理和精脱硫处理方可成为合格的焦炉气制合成天然气原料气。该公司焦化厂焦炉气的主要组成和杂质含量情况分别见表1、表2。
[0026] 表1焦炉煤气干基平均组成
表2焦炉煤气杂质指标 _
(2)焦炉煤气净化工序
一般情况下焦炉煤气在焦化厂内已进行了初步的处理,即焦炉煤气先初冷,电捕,鼓风机加压,然后氨回收和洗苯,最后经过湿法脱硫后送出界区。下游各用户再根据下游产品要求,做进一步净化处理。
[0027] 如附图1所示,本发明所述的方法中,脱苯、脱萘和脱焦油主要是通过粗脱萘及焦油、变温吸附深度净化(TSA)工序来完成。经过变温吸附(即TSA法)处理,基本可以将焦炉气中这三部分有机物彻底脱除,而脱除H2S和有机硫则是通过初脱硫段和精脱硫段两个干法脱硫过程来完成。
[0028] 由于本发明所述的方法中后续甲烷化反应采用专用的Ni系甲烷化催化剂(该专用的Ni系甲烷化催化剂由西南化工研究设计院有限公司提供,其制备方法按照授权公告号为CN101391218B的中国专利中所公开的方法)。该专用催化剂对硫极为敏感,工艺要求比较严格,原料气必须精脱硫(煤气中H2S〈 0.lppm)。为此,本发明所述的方法中所述初脱硫和所述精脱硫均采用干法脱硫;其中初脱硫采用Fe2O3脱硫剂或Fe-Mn脱硫剂或ZnO脱硫剂,所述精脱硫采用ZnO脱硫剂。通过精脱硫完全可以确保净化气中总硫小于0.1ppm或
0.lXl(T6g。
[0029] (3)0)2气化
本发明方法中所述焦炉气补碳的来源为低温液态商品CO2,所述低温液态商品CO2经过CO2气化工序转变为具有一定自压的且该压力与甲烷化压力相当的CO2气体,然后将该处于气化状态的CO2气体从焦炉气净化工序的精脱硫段连续补入三段甲烷化反应系统,所述三级甲烷化反应系统中补入的CO2气体的量为焦炉气气体体积的4%~8%。
[0030] 该液态商品CO2依托周边化肥、电厂等企业采购,其CO2组分情况见表3。
[0031] 表3 CO2组分表
甲烷化是强放热反应体系,反应放热量大,必须及时从甲烷化反应系统内移出热量,控制反应温度。因此,甲烷化催化剂的选择和甲烷化反应系统中反应温度的控制就成为了焦炉气甲烷化制合成天然气技术的两个最为关键的方面。
[0032] 本发明一种焦炉气直接补二氧化碳制合成天然气的方法中所述甲烷化工序采用三段或三段以上绝热式甲烷化反应器,甲烷化催化剂采用专用的Ni系甲烷化催化剂(该专用的Ni系甲烷化催化剂由西南化工研究设计院有限公司提供,其制备方法按照授权公告号为CN101391218B的中国专利中所公开的方法)。
[0033] 本发明所述方法的甲烷化反应系统的反应平衡、反应压力和反应放热的控制是通过按比例分配从精脱硫段出来的补充CO2后的焦炉气进行一段甲烷化反应的气体体积和进行二段甲烷化反应的气体体积以及一段甲烷化反应后气体和二段甲烷化反应后气体间的部分内循环来实现的;而该部分内循环过程则是通过在精脱硫段和二段甲烷化反应之间设置一个或多个稀释气混合器9来实现的。
[0034] 通过本发明所述方法的甲烷化反应的反应平衡、反应压力和反应放热的控制,从精脱硫段出来的补充CO2后的焦炉气进入一段甲烷化反应器的气体的量和二段甲烷化反应器的气体的量的比例为1: (I~3) (V/V),从二段甲烷化反应器出来的甲烷化后气体进入稀释气混合器的量和三段甲烷化反应器气体的量的比例为1: (I~3) (VA)0 一段甲烷化反应器10、二段甲烷化反应器12和三段甲烷化反应器14的反应温度均控制在300°C~650 0C,反应压力均控制在2.3MPa~2.7MPa。
[0035] 由于本发明所述的方法中所述三段甲烷化反应均采用绝热式反应器,甲烷化催化剂采用专用的Ni系甲烷化催化剂。因此,甲烷化反应的反应平衡、反应压力和反应放热的控制是本发明的核心技术内容。
[0036] 为了更好地控制反应放热,本发明所述的方法中所述一段、二段和三段甲烷化反应系统的热量控制还包括热量移出系统,通过所述热量的移除系统可以副产一定量的
3.8MPa、450°C的水蒸汽。所述热量的移出系统可以是一个或多个换热器。
[0037] (5)膜分离工序
甲烷化后的干气主要含有CH4、N2、H2以及微量的CO和C02。需经过膜分离工序才能将产品SNG和H2完全分离。本发明方法所述膜分离工序包括气液分离段和膜分离段,所述气液分离段设置于所述膜分离段之前,本发明所述方法的一段、二段和三段甲烷化反应过程中所产生的H2O通过所述气液分离段除去。
[0038] 本发明方法采用膜分离技术把甲烷化后气体中的绝大部分H2分离出去,可得到纯度在95%以上的H2,该部分富余的H2返回到TSA深度净化工序循环使用。
[0039] 经过膜分离以后的得到的非渗透气主要是CH4和少量的N2和H2,该非渗透气符合国家合成天然气相关标准的要求,可直接利用管网输送到用户。
[0040] 下面结合图2对本发明的最佳实施例进行具体描述。
[0041] 如图2所示,经过粗脱萘及焦油的原料焦炉气经压缩机I压缩增压至约0.6MPa,然后依次通过初脱硫器2脱硫、TSA净化器3进行深度净化、精脱硫器4脱硫,通过上述净化处理,从精脱硫段出来的焦炉气完全可以确保净化气中总硫小于0.1ppm或0.lX10_6g。
[0042] 外购的液态商品CO2储存于CO2储槽5中,经过CO2气化器6转变为具有一定自压的且该压力与甲烷化压力相当的CO2气体,然后将该处于气化状态的CO2气体与从精脱硫器4出来的焦炉气一起连续补入三段甲烷化反应系统。
[0043] 所述CO2气化器6选用水浴式气化器,所述低温液态商品CO2经过CO2气化工序转变所需的热源可以采用所述热量的移除系统副产的热水或蒸汽加热水浴式气化器。本发明方法优选采用热水加热水浴式气化器。
[0044] 经过深度净化的焦炉气和由CO2气化工序的产生的CO2气体进入精脱硫器4进行精脱硫并且完成直接补碳和焦炉气与CO2的混合过程,从精脱硫器4出来的补充CO2后的焦炉气分为两部分,一部分进入稀释气混合器9,另一部分进入二段甲烷化反应器12进行甲烷化反应;二段甲烷化反应后的气体也分为两部分,一部分进入三段甲烷化反应器14进行甲烷化反应,另一部分返回到稀释气混合器9与从精脱硫段出来的补充CO2后的焦炉气分混合,完成二段甲烷化反应后混合气体中的CH4的稀释,经稀释的混合气体从稀释气混合器9出来后进入一段甲烷化反应器10进行甲烷化反应,一段甲烷化反应器10中经过甲烷化反应的气体进入二段甲烷化反应器12与从精脱硫器4出来的进入二段甲烷化反应器12的补充CO2后的焦炉气再次进行气体稀释并完成甲烷化反应。
[0045] 上述过程中,为了进一步控制甲烷化反应体系的压力,防止气路的串通,在从精脱硫器4出来的补充CO2后的两部分焦炉气气路中设置有止回阀i 7、止回阀ii 8,具体而言,所述止回阀i 7设置于进入二段甲烷化反应器12的气路中,用于防止从一段甲烷化反应器10过来的气体进入精脱硫器4中,所述止回阀ii 8设置于进入稀释气混合器9的气路中,用于防止从二段甲烷化反应器12过来的气体进入精脱硫器4中。
[0046] 通过本发明所述方法的甲烷化反应的反应平衡、反应压力和反应放热的控制,从精脱硫器4出来的补充CO2后的焦炉气进入一段甲烷化反应器10的气体的量和二段甲烷化反应器12的气体的量的比例为1: (I~3) (V/V),从二段甲烷化反应器12出来的甲烷化后气体进入稀释气混合器9的量和三段甲烷化反应器14气体的量的比例为1: (I~3)(V/V)0 一段甲烷化反应器10、二段甲烷化反应器12和三段甲烷化反应器14的反应温度均控制在300°C~650°C,反应压力均控制在2.3MPa~2.7MPa。
[0047] 本发明所述方法中,所述二段甲烷化反应器12优选采用串联的两级甲烷化反应器,这样整个甲烷化反应系统的反应平衡、反应压力和反应放热的控制效果更优。
[0048] 经过三段甲烷化反应的混合气体,进入压缩机16再次压缩提压,然后经过气液分离器17脱水,膜分离装置18分离CH4和H2,即可得到产品SNG。
[0049] 为了更好地控制反应放热,本发明所述的方法中一段甲烷化反应器10和二段甲烷化反应器12之间设置有换热装置I 11、二段甲烷化反应器12和三段甲烷化反应器14之间设置有换热装置II 13以及三段甲烷化反应器14和压缩机16之间设置有换热装置III15。通过所述换热装置I 11、换热装置II 13、换热装置III 15,本发明方法所述的三段甲烷化反应系统可以副产一定量的3.8MPa、450°C的水蒸汽。
[0050] 以上所述仅为本发明实施例的优选方式而已,本发明并不限于上述实施例,对于本领域技术人员来说,本发明可以有各种变换和替换,例如甲烷化反应可以为四段及其以上,同时甲烷化反应器间气体的部分内循环也并不局限于一段与二段反应器之间。因此。凡在本实施例的原则和精神下所做的任何修改、等同替换、改进等,都属于本发明的保护范
围。`
Claims (10)
1.一种焦炉气直接补二氧化碳制合成天然气的方法,该方法的主要工序包含焦炉气压缩、净化、CO2气化、甲烷化和膜分离,所述焦炉气净化由初脱硫段、变温吸附深度净化段和精脱硫段组成,所述甲烷化工序采用由一段甲烷化反应器(10)、二段甲烷化反应器(12)和三段甲烷化反应器(14)组成的三段甲烷化反应系统,所述三段甲烷化反应系统中的各段甲烷化反应器均采用绝热式反应器,所述甲烷化催化剂采用专用的Ni系甲烷化催化剂,其特征在于:本发明所述方法中,进入一段甲烷化反应器(10)的焦炉气和二段甲烷化反应器(12)的焦炉气为从精脱硫段出来的补充CO2后的焦炉气;所述三段甲烷化反应系统的反应平衡、反应压力及反应放热的控制是通过按比例分配进入一段甲烷化反应器(10)的焦炉气和二段甲烷化反应器(12)的焦炉气的气体体积,以及一段甲烷化反应后的气体和二段甲烷化反应后的气体之间的部分循环来实现的;该气体之间的部分循环是通过在精脱硫段和二段甲烷化反应器(12)之间设置一个或多个稀释气混合器(9)来实现的。
2.根据权利要求1所述的一种焦炉气直接补二氧化碳制合成天然气的方法,其特征在于:所述二段甲烷化反应器(12)采用串联的两级甲烷化反应器。
3.根据权利要求1或2所述的一种焦炉气直接补二氧化碳制合成天然气的方法,其特征在于:本发明所述方法中的甲烷化反应的反应平衡、反应压力和反应放热的控制,从精脱硫段出来的补充CO2后的焦炉气进入一段甲烷化反应器(10)的气体和二段甲烷化反应器(12)的气体的体积比例为1: (I~3),从二段甲烷化反应器(12)出来的甲烷化后气体进入稀释气混合器(9)的气体和三段甲烷化反应器(14)的气体的体积比例为1: (I~3)。
4.根据权利要求1或2所述的一种焦炉气直接补二氧化碳制合成天然气的方法,其特征在于:所述焦炉气补碳的来源为低温液态商品CO2,所述低温液态商品CO2经过CO2气化工序转变为具有自压的CO2气体,然后将该处于气态的CO2气体从精脱硫段连续补入甲烷化反应系统,所述三段甲烷化反应系统中补入的CO2气体的体积为所述焦炉气气体体积的4%~8% ο
5.根据权利要求4所述的一种焦炉气直接补二氧化碳制合成天然气的方法,其特征在于:所述低温液态商品CO2经过CO2气化工序转变为具有自压的CO2气体是通过水浴式气化器完成的。
6.根据权利要求5所述的一种焦炉气直接补二氧化碳制合成天然气的方法,其特征在于:所述方法的三段甲烷化反应系统的热量控制还包括热量移出系统,通过所述热量移除系统副产3.8MPa、450°C的水蒸汽,另一部分具有一定热量的循环热水则补入水浴式气化器,用于CO2气化工序,从而形成甲烷化移热系统热量的梯级利用。
7.根据权利要求1或2所述的一种焦炉气直接补二氧化碳制合成天然气的方法,其特征在于:通过本发明所述方法的三段甲烷化反应系统的反应平衡、反应压力和反应放热的控制,一段甲烷化反应器(10)、二段甲烷化反应器(12)和三段甲烷化反应器(14)的操作温度均控制在300°C~650°C,反应压力均控制在2.3MPa~2.7MPa。
8.根据权利要求1或2所述的一种焦炉气直接补二氧化碳制合成天然气的方法,其特征在于:所述初脱硫段和精 脱硫段均采用干法脱硫,其中所述初脱硫段采用Fe2O3脱硫剂或Fe-Mn脱硫剂或ZnO脱硫剂,所述精脱硫段采用ZnO脱硫剂。
9.根据权利要求1或2所述的一种焦炉气直接补二氧化碳制合成天然气的方法,其特征在于:所述膜分离工序包括由压缩机(16)和气液分离器(17)顺次连接组成的气液分离段和由膜分离装置(18)组成的膜分离段,所述气液分离段设置于所述膜分离段之前,本发明所述方法的三段甲烷化反应系统在甲烷化反应过程中所产生的H2O通过所述气液分离段除去。
10.根据权利要求1或2所述的一种焦炉气直接补二氧化碳制合成天然气的方法,其特征在于:经过膜 分离工序后产生的富余H2返回到变温吸附深度净化工序循环使用。
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