CN111256431B - 一种混合冷剂沼气带压液化系统及其工作方法 - Google Patents

一种混合冷剂沼气带压液化系统及其工作方法 Download PDF

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CN111256431B
CN111256431B CN202010091218.8A CN202010091218A CN111256431B CN 111256431 B CN111256431 B CN 111256431B CN 202010091218 A CN202010091218 A CN 202010091218A CN 111256431 B CN111256431 B CN 111256431B
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mixed refrigerant
outlet
stage compressor
heat exchanger
membrane separator
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CN111256431A (zh
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王勇
常明亮
全青
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Xian Shiyou University
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Abstract

本发明公开的一种混合冷剂沼气带压液化系统及其工作方法，属于沼气液化技术领域。包括沼气预处理单元、二级膜分离单元、混合冷剂制冷循环单元和CO2精馏提纯单元，沼气经沼气预处理单元脱硫、脱水、过滤后加压，经二级膜分离单元得到高纯度CH4流和富CO2流沼气，经带压液化和精馏，得到带压液态CH4和食品级液态CO2。该系统设计合理、自动化程度高，用于解决当前沼气液化工艺中原料气脱碳工艺复杂、脱碳指标苛刻、碳资源浪费等问题，具有良好的应用前景。

Description

一种混合冷剂沼气带压液化系统及其工作方法
技术领域
本发明属于沼气液化技术领域，具体涉及一种混合冷剂沼气带压液化系统 及其工作方法。
背景技术
我国近十年来开始逐渐重视和发展沼气产业，积极推动沼气行业向生物天 然气行业发展。然而，随着我国沼气工程逐渐向大中型方向发展，丰富的沼气 资源面临着后续消纳的问题，特别是在难以并入天然气管网、发电并网等情况 下，这一问题更加突出。利用天然气液化技术将沼气液化供应给周边LNG加气 站和城市居民是实现沼气的近距离输送和商业化应用的一种方式。
但沼气中含有大量的CO2，给液化带来了很大的困难。较多学者设计了各种 沼气液化工艺，但都属于常规的沼气液化流程，需要脱除原料气中的CO2，这不 仅需要复杂的碳脱除工艺，而且浪费了沼气中丰富的碳资源。
发明内容
为了解决上述现有技术中存在的缺陷，本发明的目的在于提供一种混合冷 剂沼气带压液化系统及其工作方法，系统设计合理、自动化程度高，用于解决 常规的沼气液化流程需要脱除原料气中的CO2所带来的碳脱除工艺冗杂和碳资 源浪费等问题。
本发明通过以下技术方案来实现：
本发明公开了一种混合冷剂沼气带压液化系统，包括沼气预处理单元、二 级膜分离单元、混合冷剂制冷循环单元和CO2精馏提纯单元；
沼气预处理单元包括依次连接的活性炭脱硫塔、低压压缩机、分子筛和精 过滤器，活性炭脱硫塔连接有沼气进气管；
二级膜分离单元包括分离前多级压缩机组、一级膜分离器、二级膜分离器、 第一混合器和渗透侧多级压缩机组；分离前多级压缩机组的进气口与精过滤器 的出口连接，分离前多级压缩机组的出气口与一级膜分离器的进气口连接，一 级膜分离器的渗余侧出口与二级膜分离器的进气口连接，一级膜分离器的渗透 侧出口与第一混合器的入口连接，二级膜分离器渗透侧出口与第一混合器的入 口连接，第一混合器的出口与渗透侧多级压缩机组的进气口连接；
混合冷剂制冷循环单元包括第二混合器、混合冷剂多级压缩机组、换热器、 节流阀和液态CH4储罐；第二混合器接有若干冷剂管道，第二混合器出气口与 混合冷剂多级压缩机组的进气口连接，混合冷剂多级压缩机组的出气口与换热 器的热端入口连接，换热器的热端出口与节流阀的进料口连接，节流阀的出料 口与换热器的冷端入口连接，换热器的冷端出口与第二混合器连接，换热器的 热端出口与液态CH4储罐连接；换热器的热端入口分别与渗透侧多级压缩机组 的出气口和二级膜分离器的渗余侧出口连接；
CO2精馏提纯单元包括精馏塔、冷凝器、放空火炬、再沸器和液态CO2储 罐；精馏塔的进料口与换热器的热端出口连接，精馏塔的塔顶与冷凝器进料口 连接，冷凝器出料口接入换热器的冷端入口，换热器的冷端出口与放空火炬连 接，精馏塔的塔釜与再沸器的进料口连接，再沸器的出料口与液态CO2储罐连 接。
优选地，分离前多级压缩机组包括分离前一级压缩机和分离前二级压缩机， 分离前一级压缩机的进气口与精过滤器的出口连接，分离前一级压缩机的出气 口与分离前二级压缩机的进气口连接，分离前二级压缩机的出气口与一级膜分 离器的进气口连接。
优选地，渗透侧多级压缩机组包括渗透侧一级压缩机和渗透侧二级压缩机， 渗透侧一级压缩机的进气口与第一混合器的出口连接，渗透侧一级压缩机的出 气口与渗透侧二级压缩机的进气口连接，渗透侧二级压缩机的出气口与换热器 的热端入口连接。
优选地，混合冷剂多级压缩机组包括依次连接的混合冷剂一级压缩机、混 合冷剂二级压缩机、混合冷剂三级压缩机和混合冷剂四级压缩机，混合冷剂一 级压缩机的进气口与第二混合器出气口连接，混合冷剂四级压缩机的出气口与 换热器的热端入口连接。
本发明公开了上述混合冷剂沼气带压液化系统的工作方法，包括：
沼气由沼气进气管进入活性炭脱硫塔脱除H2S，然后经低压压缩机压缩冷却 进入分子筛深度脱水，再经精过滤器脱除固体颗粒得到净化气；
净化气经分离前多级压缩机组加压后进入一级膜分离器，渗余侧气体进入 二级膜分离器，渗透侧气体进入第一混合器，二级膜分离器的渗余侧气体进入 换热器液化，二级膜分离器的渗透侧气体进入第一混合器；第一混合器出气进 入渗透侧多级压缩机组加压后进入换热器；
多种冷剂循环介质经第二混合器混合后进入混合冷剂多级压缩机组压缩后 进入换热器冷却后，经节流阀节流，CH4流和富CO2流在换热器中液化，液态 CH4引入液态CH4储罐存储；
富CO2流进入精馏塔，塔底精馏后的高纯度液态CO2经再沸器后引入液态 CO2储罐存储，塔顶的CH4/CO2混合气经换热器回收冷量后在放空火炬中燃烧。
优选地，净化气的主要成分为CH4和CO2。
优选地，冷剂循环介质为C1、C2、C3和N2。
优选地，一级膜分离器和二级膜分离器的分离压差均为1～1.2MPa，经一级 膜分离器和二级膜分离器的分离后，二级膜分离器的渗余侧气体CH4纯度为 98.5％-99.5％。
优选地，净化气在分离前多级压缩机组中升压至2MPa，一级膜分离器和二 级膜分离器渗透侧富CO2流经多渗透侧多级压缩机组升压至2.8MPa。
优选地，再沸器的出料产品纯度＞99.95％，冷凝器的冷凝温度＞56℃。
与现有技术相比，本发明具有以下有益的技术效果：
本发明公开的一种混合冷剂沼气带压液化系统，包括沼气预处理单元、二 级膜分离单元、混合冷剂制冷循环单元和CO2精馏提纯单元，沼气经沼气预处理 单元脱硫、脱水、过滤后加压，经二级膜分离单元得到高纯度的CH4和富CO2沼 气，经带压液化和精馏，得到带压液态CH4和食品级液态CO2。该系统设计合理、 自动化程度高，用于解决当前沼气液化工艺中原料气脱碳工艺复杂、脱碳指标 苛刻、碳资源浪费等问题，具有良好的应用前景。
进一步地，目前工业用压缩机设备一次增压虽可实现较大的压力提升，但 致使气体温度剧烈上升，一次增压的能耗也急剧增加，所以经济来讲，目前多 采用多级压缩的方式进行气体增压，级间进行气体冷却以减小能耗，分离前多 级压缩机组、渗透侧多级压缩机组和混合冷剂多级压缩机组均采用多级压缩机。
本发明公开了上述混合冷剂沼气带压液化系统的工作方法，利用吸附过滤 技术、膜分离技术、带压液化技术和精馏技术，得到了高纯度CH4和食品级液态 CO2，自动化程度高，能够与现有的成熟工业系统良好兼容。
进一步地，冷剂循环介质采用C1、C2、C3和N2，来源广泛，价格合理，能 满足工艺要求。
进一步地，目前工业应用中要求膜分离压差在1～1.2Ma左右，压差过小无法 满足分离要求。二级膜分离后的渗余侧气体纯度为98.5％-99.5％，防止CH4带压 液化过程中CO2发生冻堵。
进一步地，净化气分离前增压至2MPa，一是为了增强膜分离效果，二是参 考了当前成熟的膜分离工艺参数的设定；渗透侧富CO2气体增压至2.8MPa，一是 为了便于气体在冷箱中液化，减少能耗，二是参考了当前成熟的富CO2气体液化、 精馏工艺参数的设定。
进一步地，再沸器的出料产品纯度＞99.95％，能够满足食品级液态CO2的国 家标准，使产品多元化；冷凝器的冷凝温度＞56℃，是因为冷凝器中CO2含量较 高，与压力相比，其发生CO2冻堵的温度敏感性更高，根据CH4和CO2的二元相 图可知，当温度大于56℃时，在可控的压力范围内，基本没有CO2冻堵风险。
附图说明
图1为本发明的混合冷剂沼气带压液化系统的整体结构示意图；
图2为采用软件对本发明的系统进行模拟和优化的流程图。
图中：1-活性炭脱硫塔，2-低压压缩机，3-分子筛，4-精过滤器，5-分离前 一级压缩机，6-分离前二级压缩机，7-一级膜分离器，8-第一混合器，9-二级膜 分离器，11-渗透侧一级压缩机，12-渗透侧二级压缩机，13-精馏塔，14-冷凝器， 15-再沸器，16-液态CO2储罐，17-液态CH4储罐，18-第二混合器，19-混合冷剂 一级压缩机，20-混合冷剂二级压缩机，21-混合冷剂三级压缩机，22-混合冷剂 四级压缩机，23-换热器，23-1-换热器第一冷端，23-2-换热器第二冷端，23-3- 换热器第一热端，23-4-换热器第二热端，23-5-换热器第三热端，24-节流阀，25 放空火炬。
具体实施方式
下面结合附图和具体实施例对本发明做进一步详细描述，其内容是对本发 明的解释而不是限定：
如图1，本发明的混合冷剂沼气带压液化系统，包括沼气预处理单元、二级 膜分离单元、混合冷剂制冷循环单元和CO2精馏提纯单元；
沼气预处理单元包括依次连接的活性炭脱硫塔1、低压压缩机2、分子筛3 和精过滤器4，活性炭脱硫塔1连接有沼气进气管；
二级膜分离单元包括分离前多级压缩机组、一级膜分离器7、二级膜分离器 9、第一混合器8和渗透侧多级压缩机组；分离前多级压缩机组的进气口与精过 滤器4的出口连接，分离前多级压缩机组包括分离前一级压缩机5和分离前二 级压缩机6，分离前一级压缩机5的进气口与精过滤器4的出口连接，分离前一 级压缩机5的出气口与分离前二级压缩机6的进气口连接，分离前二级压缩机6 的出气口与一级膜分离器7的进气口连接；一级膜分离器7的渗透侧出气口与 第一混合器8连接，一级膜分离器7的渗余侧出气口与二级膜分离器9的进气 口连接，二级膜分离器9的渗透侧出口与第一混合器8连接；渗透侧多级压缩 机组包括渗透侧一级压缩机11和渗透侧二级压缩机12，渗透侧一级压缩机11 的进气口与第一混合器8出气口连接，渗透侧一级压缩机11的出气口与渗透侧 二级压缩机12的进气口连接，渗透侧二级压缩机12的出气口与换热器第三热 端23-5的入口连接。
混合冷剂制冷循环单元包括第二混合器18、混合冷剂多级压缩机组、换热 器23、节流阀24和液态CH4储罐17；节流阀24可采用J-T节流阀；第二混合 器18接有若干冷剂管道，混合冷剂多级压缩机组包括依次连接的混合冷剂一级 压缩机19、混合冷剂二级压缩机20、混合冷剂三级压缩机21和混合冷剂四级 压缩机22，混合冷剂一级压缩机19的进气口与第二混合器18出气口连接，混 合冷剂四级压缩机22的出气口与换热器第一热端23-3的入口连接，第一热端 23-3的出口与节流阀24的进料口连接，节流阀24的出料口与与换热器第二冷 端23-2的入口连接，换热器第二冷端23-2的出口与第二混合器18连接，换热 器第二热端23-4的出口与液态CH4储罐17连接；换热器第二热端23-4的入口 与二级膜分离器9的渗余侧出气口连接。
CO2精馏提纯单元包括精馏塔13、冷凝器14、放空火炬25、再沸器15和 液态CO2储罐16；精馏塔13的进料口与换热器第三热端23-5的出口连接，精 馏塔13的塔顶与冷凝器14进料口连接，冷凝器14出料口接入换热器第一冷端23-1的入口，换热器第一冷端23-1的出口与放空火炬25连接，精馏塔13的塔 釜与再沸器15的进料口连接，再沸器15的出料口与液态CO2储罐16连接。
上述混合冷剂沼气带压液化系统在工作时：
沼气由沼气进气管进入活性炭脱硫塔1脱除少量H2S，然后经低压压缩机2 压缩冷却进入分子筛3深度脱水，再经精过滤器4脱除固体颗粒得到净化气， 气质组成主要包含CH4和CO2。
净化气经分离前多级压缩机组升压至2MPa后进入一级膜分离器7，其渗余 侧气体进入二级膜分离器9，其渗余侧气体CH4浓度控制在98.5％-99.5％，随后 进入换热器23带压液化，一级膜分离器7和二级膜分离器9的渗透侧气体(富 CO2流)混合后经多级压缩机组升压至2.8MPa后进入换热器液化；一级膜分离 器7和二级膜分离器9的分离压差均介于1～1.2MPa。
多种冷剂循环介质经第二混合器18混合后进入混合冷剂多级压缩机组压缩 后进入换热器23冷却后，经节流阀24节流，98.5％-99.5％纯度的CH4流和富 CO2流在换热器23中液化，液态CH4引入液态CH4储罐17存储。
富CO2流进入精馏塔13，塔底精馏后的高纯度液态CO2经再沸器15后引 入液态CO2储罐16存储，塔顶的少量CH4/CO2混合气经冷凝器14回收冷量后 在放空火炬25中放空燃烧。
为了进一步评价该系统的工艺参数和适应性，使用HSYSY软件和Matlab 软件对系统工艺进行了模拟和优化，如图2。对于沼气产量1000kg/h的大中型 沼气工程，假设净化气的组成为60％CH4+40％CO2，该系统可实现沼气液化率 84.24％、CH4回收率83.62％、CO2回收率85.17％、液态CH4产出率51.06％、 液态CO2产出率33.18％。按当前市场情况，LNG和食品级液态CO2的价格分别 约为4.4元/kg、12元/kg产品总销售额7797元/h。在此基础上，建立了HYSYS &Matlab混合仿真平台，以产品比功耗为目标函数，冷剂流量、冷剂高压、节 流膨胀温度为优化变量，采用序列二次规划(SQP)算法，对工艺进行了优化， 优化后的产品比功耗为0.2982kW·h/kg，C1流量14.84kgmole/h，C2流量7.945 kgmole/h，C3流量47kgmole/h，N2流量4.74kgmole/h，混合冷剂高压4.796MPa， 节流膨胀后温度-125℃。考虑到沼气的气质组成和生产速率受温度、搅拌方式、 原料配比等因素的影响，所以通过调整沼气组分(CH4 57％～62％)和流量(920 kg/h～1060kg/h)，分析了优化工况的适应性，模拟显示沼气液化率等性能指标波 动范围不超过6％。在模拟过程中，根据当前工艺应用现状，部分关键工艺参数 如下：进料温度为30℃，进料压力为500kPa，进料流量为1000kg/h，物性模 拟流体包为GERG-2008，水冷器冷却温度为30℃，水冷器/换热器压降为10 kPa，最小换热温差为3℃，压缩机等熵效率为85％，膜分离器为醋酸纤维膜 (PCO2＝2.43Barrer，aCO2/CH4＝22.1)。
需要说明的是，以上所述仅为本发明实施方式的一部分，根据本发明所描 述的系统所做的等效变化，均包括在本发明的保护范围内。本发明所属技术领 域的技术人员可以对所描述的具体实例做类似的方式替代，只要不偏离本发明 的结构或者超越本权利要求书所定义的范围，均属于本发明的保护范围。

Claims (10)

1.一种混合冷剂沼气带压液化系统，其特征在于，包括沼气预处理单元、二级膜分离单元、混合冷剂制冷循环单元和CO2精馏提纯单元；
沼气预处理单元包括依次连接的活性炭脱硫塔(1)、低压压缩机(2)、分子筛(3)和精过滤器(4)，活性炭脱硫塔(1)连接有沼气进气管；
二级膜分离单元包括分离前多级压缩机组、一级膜分离器(7)、二级膜分离器(9)、第一混合器(8)和渗透侧多级压缩机组；分离前多级压缩机组的进气口与精过滤器(4)的出口连接，分离前多级压缩机组的出气口与一级膜分离器(7)的进气口连接，一级膜分离器(7)的渗余侧出口与二级膜分离器(9)的进气口连接，一级膜分离器(7)的渗透侧出口与第一混合器(8)的入口连接，二级膜分离器(9)渗透侧出口与第一混合器(8)的入口连接，第一混合器(8)的出口与渗透侧多级压缩机组的进气口连接；
混合冷剂制冷循环单元包括第二混合器(18)、混合冷剂多级压缩机组、换热器(23)、节流阀(24)和液态CH4储罐(17)；第二混合器(18)接有若干冷剂管道，第二混合器(18)出气口与混合冷剂多级压缩机组的进气口连接，混合冷剂多级压缩机组的出气口与换热器(23)的热端入口连接，换热器(23)的热端出口与节流阀(24)的进料口连接，节流阀(24)的出料口与换热器(23)的冷端入口连接，换热器(23)的冷端出口与第二混合器(18)连接，换热器(23)的热端出口与液态CH4储罐(17)连接；换热器(23)的热端入口分别与渗透侧多级压缩机组的出气口和二级膜分离器(9)的渗余侧出口连接；
CO2精馏提纯单元包括精馏塔(13)、冷凝器(14)、放空火炬(25)、再沸器(15)和液态CO2储罐(16)；精馏塔(13)的进料口与换热器(23)的热端出口连接，精馏塔(13)的塔顶与冷凝器(14)进料口连接，冷凝器(14)出料口接入换热器(23)的冷端入口，换热器(23)的冷端出口与放空火炬(25)连接，精馏塔(13)的塔釜与再沸器(15)的进料口连接，再沸器(15)的出料口与液态CO2储罐(16)连接。
2.根据权利要求1所述的混合冷剂沼气带压液化系统，其特征在于，分离前多级压缩机组包括分离前一级压缩机(5)和分离前二级压缩机(6)，分离前一级压缩机(5)的进气口与精过滤器(4)的出口连接，分离前一级压缩机(5)的出气口与分离前二级压缩机(6)的进气口连接，分离前二级压缩机(6)的出气口与一级膜分离器(7)的进气口连接。
3.根据权利要求1所述的混合冷剂沼气带压液化系统，其特征在于，渗透侧多级压缩机组包括渗透侧一级压缩机(11)和渗透侧二级压缩机(12)，渗透侧一级压缩机(11)的进气口与第一混合器(8)的出口连接，渗透侧一级压缩机(11)的出气口与渗透侧二级压缩机(12)的进气口连接，渗透侧二级压缩机(12)的出气口与换热器(23)的热端入口连接。
4.根据权利要求1所述的混合冷剂沼气带压液化系统，其特征在于，混合冷剂多级压缩机组包括依次连接的混合冷剂一级压缩机(19)、混合冷剂二级压缩机(20)、混合冷剂三级压缩机(21)和混合冷剂四级压缩机(22)，混合冷剂一级压缩机(19)的进气口与第二混合器(18)出气口连接，混合冷剂四级压缩机(22)的出气口与换热器(23)的热端入口连接。
5.根据权利要求1～4任意一项所述混合冷剂沼气带压液化系统的工作方法，其特征在于，包括：
沼气由沼气进气管进入活性炭脱硫塔(1)脱除H2S，然后经低压压缩机(2)压缩冷却进入分子筛(3)深度脱水，再经精过滤器(4)脱除固体颗粒得到净化气；
净化气经分离前多级压缩机组加压后进入一级膜分离器(7)，渗余侧气体进入二级膜分离器(9)，渗透侧气体进入第一混合器(8)，二级膜分离器(9)的渗余侧气体进入换热器(23)液化，二级膜分离器(9)的渗透侧气体进入第一混合器(8)；第一混合器(8)出气进入渗透侧多级压缩机组加压后进入换热器(23)；
多种冷剂循环介质经第二混合器(18)混合后进入混合冷剂多级压缩机组压缩后进入换热器(23)冷却后，经节流阀(24)节流，CH4流和富CO2流在换热器(23)中液化，液态CH4引入液态CH4储罐(17)存储；
富CO2流进入精馏塔(13)，塔底精馏后的高纯度液态CO2经再沸器(15)后引入液态CO2储罐(16)存储，塔顶的CH4/CO2混合气经换热器(23)回收冷量后在放空火炬(25)中燃烧。
6.根据权利要求5所述的混合冷剂沼气带压液化系统的工作方法，其特征在于，净化气的主要成分为CH4和CO2。
7.根据权利要求5所述的混合冷剂沼气带压液化系统的工作方法，其特征在于，冷剂循环介质为C1、C2、C3和N2。
8.根据权利要求5所述的混合冷剂沼气带压液化系统的工作方法，其特征在于，一级膜分离器(7)和二级膜分离器(9)的分离压差均为1～1.2MPa，经一级膜分离器(7)和二级膜分离器(9)的分离后，二级膜分离器(9)的渗余侧气体CH4纯度为98.5％-99.5％。
9.根据权利要求5所述的混合冷剂沼气带压液化系统的工作方法，其特征在于，净化气在分离前多级压缩机组中升压至2MPa，一级膜分离器(7)和二级膜分离器(9)渗透侧富CO2流经多渗透侧多级压缩机组升压至2.8MPa。
10.根据权利要求5所述的混合冷剂沼气带压液化系统的工作方法，其特征在于，再沸器(15)的出料产品纯度＞99.95％，冷凝器(14)的冷凝温度＞56℃。
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