CN113686098B - 一种天然气液化及氦气回收方法 - Google Patents

一种天然气液化及氦气回收方法 Download PDF

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CN113686098B
CN113686098B CN202111133505.1A CN202111133505A CN113686098B CN 113686098 B CN113686098 B CN 113686098B CN 202111133505 A CN202111133505 A CN 202111133505A CN 113686098 B CN113686098 B CN 113686098B
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CN113686098A (zh
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蒋洪
李浩玉
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Southwest Petroleum University
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Abstract

本发明公开了一种天然气液化及氦气回收方法，将天然气液化与氦回收集成，提出了一种天然气液化及氦气回收的方法，该方法将氦气回收塔与脱氮塔塔底部分出料分别集成于主冷箱和氦回收冷箱内为两塔提供冷源，取消了脱氮塔和氦气回收塔重沸器，简化了流程，提高了系统热集成度。原料气降温后进入重烃分离器，重烃分离器气相进入主冷箱降温后进入闪蒸罐，浓缩氦回收塔进料，闪蒸罐气相增压后降温进入氦气回收塔进行氦气回收，闪蒸罐液相进入脱氮塔进行脱氮。脱氮塔顶气相经换热后进入压缩系统，增压后的高纯度氮气一部分作为制冷剂，另一部分可作为工业用途。本发明具有系统热集成度高、能耗低，投资小，天然气液化率及氦气回收率高等特点。

Description

一种天然气液化及氦气回收方法
技术领域
本发明涉及天然气加工工艺技术领域，特别涉及一种天然气液化及氦气回收方法。
背景技术
氦主要用于低温超导、航空航天、半导体、光纤等技术领域，我国氦气资源贫乏，进口需求量大，含氦天然气是工业生产氦气的主要来源，建设天然气氦气回收工程有利于缓解我国氦气进口压力，本文提出的天然气液化及氦气回收方法对建设天然气提氦工程具有积极技术支撑作用。
专利CN109734064《一种氦气生产系统和生产方法》中徐鹏等人提出了从BOG中提取氦气的方法，该系统并没有将天然气液化与提氦进行集成，重沸器位于在氦气回收塔内部，导致冷热物流换热匹配度较差，不利于能量的有效利用。
专利CN112066642A《一种高含氮和含氦天然气液化及粗氦和氮气提取系统》发明者魏义江等人提出了高含氮和含氦天然气液化及提氦系统，该系统预处理后的天然气依次经过脱甲烷塔和脱氮塔，原料气中氮气在流程中，两次冷凝和一次蒸发，脱甲烷塔塔底的热负荷与脱氮塔塔顶的冷负荷增加，导致系统能耗增加。该系统制冷方式采用单一混合冷剂三级节流制冷，制冷系统提供的温位变化较大，变化范围从40℃降低至-180℃，制冷剂循环量较大。该系统中重沸器位于塔内部，依靠高温位的混合冷剂提供所需的热量，重沸器所需温位与高温制冷剂温差较大，导致换热的
Figure GDA0003636552190000011
损失增加。另外，流程系统复杂，设备较多。
天然气液化、脱氮及提氦工艺具有一定的相似性，通过热集成的方式可充分减少设备，降低能耗，现有专利中联产工艺研究较少，且现有工艺联产工艺中脱氮塔及氦气回收塔的形式不利于能量的充分利用。
发明内容
针对现有天然气氦气回收方法存在的高能耗、氦气回收率低以及粗氦产品纯度低的问题，本发明提供了一种天然气氦气回收及天然气液化联产的方法，开发了一种天然气提氦及天然气液化流程，该流程适用于不同氦气含量的含氦天然气氦气回收及天然气液化系统，特别适合于天然气中氦气含量低的氦气回收及天然气液化系统。该流程中原料气通过预冷器(E-101)预冷，主冷箱(E-102)降温液化进入重烃分离器(V-101)分离出部分重烃，重烃分离器液相预冷原料气后去外输，重烃分离器气相经主冷箱(E-102)降温节流后进入闪蒸罐(V-102)。闪蒸罐(V-102)气相经主冷箱和氦回收冷箱冷凝节流后作为氦气回收塔中部进料，闪蒸罐(V-102)液相进入脱氮塔脱氮。氦气回收塔(T-102)和脱氮塔(T-101)塔底重沸器热源采用塔底出料部分物流复热的方式作为塔器塔底进料。天然气液化及氦气回收工艺流程如图1所示。
本发明提供的天然气液化及氦气回收的联产方法，其工艺流程特征如下：
(1)将天然气液化及氦气回收工艺进行耦合，经预处理后的天然气进入预冷器(E-101)预冷、主冷箱(E-102)降温进入重烃分离器(V-101)，重烃分离器液相预冷原料气后去外输，重烃分离器气相经主冷箱(E-102)降温节流降压后进入闪蒸罐(V-102)，闪蒸罐气相作为含氦原料气，闪蒸罐液相经泵(P-104)增压后进入脱氮塔(T-101)脱氮。
(2)含氦原料气通过增压(K-101)分别进入主冷箱、氦回收冷箱降温后进入氦气回收塔(T-102)中部。氦气回收塔热源来源于塔底出料部分物流与氦回收冷箱换热升温复热的负荷，氦气回收塔塔顶气相在冷凝器(E-104)经降温节流后的低温高纯度氮气降温部分冷凝回流，氦气回收塔塔顶气相经氦回收冷箱复热后作为粗氦产品(氦气含量70％以上)进入后续处理单元提纯。
(3)制冷循环采用混合冷剂制冷循环与高纯氮气制冷循环的双循环制冷，混合冷剂为天然气液化提供冷量，高纯氮气制冷循环为天然气液化及脱氮塔和氦回收塔提供冷量。天然气处理量较小时(小于50×104m3/d)，制冷循环采用混合冷剂与氮气制冷循环构成的双循环，其流程图如图1所示。
(4)流程中主冷箱(E-102)采用多股板翅式换热器，将八股热流与三股冷流集成于主冷箱(E-102)中。主冷箱的八股热流分别为原料气、混合冷剂制冷循环2股、高纯度氮气制冷循环1股、重烃分离器(V-101)气相物流、闪蒸罐(V-102)气相增压物流、氦气回收塔回流物流、脱氮塔塔底去生产LNG凝液；主冷箱的三股冷流分别为高纯氮气产品物流、混合冷剂1股，脱氮塔底凝液复热物流。
(5)流程中氦回收冷箱(E-103)采用多股板翅式换热器，将两股热流与四股冷流集成于深冷冷箱(E-103)中。氦回收冷箱的两股热流为原料气物流、氮气冷剂制冷循环1股，四股冷流分别为氮气冷剂制冷循环1股、氦气回收塔底出料物流2股。
(6)对于不同处理规模的天然气液化及氦气回收装置，系统能耗与天然气处理规模和制冷循环工艺有关，当天然气处理量较大时(大于50×104m3/d)，可优选制冷系统，本发明的天然气液化及氦气回收系统工艺方案及总体技术路线保持不变，仅改变天然气液化制冷循环。
与现有技术相比，本发明的有益之处在于：
(1)本发明将天然气液化、脱氮与氦回收工艺集成，简化工艺流程，大幅减少了工艺设备投资。
(2)氦气回收塔与脱氮塔不单独设置重沸器，两塔重沸器热源分别来源于塔底出料部分物流与主冷箱和氦回收冷箱换热升温复热的负荷，简化了流程，提高了系统热集成度，降低了系统的
Figure GDA0003636552190000031
损失。
(3)制冷循环采用混合冷剂制冷循环与高纯氮气制冷循环的双循环制冷，流程中制冷温位与系统热物流相匹配，减少了制冷系统负荷。
(4)氦气回收率与粗氦产品纯度高，且回收率可调，流程适应性强。
(5)高纯度氮气制冷剂来源于天然气，不需要额外购买，同时可获得高纯度氮气作为工业用途。
(6)当天然气中氮气含量低于3％(摩尔百分数)时，取消脱氮塔(T-101)，增设闪蒸罐(V-103)，其流程见图2。
本发明的优点、目标和特征将通过运用实例说明，有利于技术人员增强理解。
附图说明
下面结合附图和具体实施方式对本范明作进一步详细的说明
图1为实例1：高含氮天然气液化及氦气回收工艺流程图；
其中，E-101-预冷器；E-102-主冷箱；E-103-氦回收冷箱；E-104-冷凝器；V-101-重烃分离器；V-102-闪蒸罐；K-101-闪蒸气压缩机；T-101-脱氮塔；T-102-氦气回收塔；P-101-泵；S-101-LNG储罐；
图2为实例2：低含氮天然气液化及氦气回收工艺流程图；
其中，E-101-预冷器；E-102-主冷箱；E-103-氦回收冷箱；E-104-冷凝器；V-101-重烃分离器；V-102-闪蒸罐；V-103-闪蒸罐；K-101-闪蒸气压缩机；T-102-氦气回收塔；S-101-LNG储罐；
具体实施方式
下面结合附图对本发明的实例进行说明，应当理解，此处所描述的实例仅用于说明和解释本发明，并不用于限定本发明。实例中压力采用绝压。
实例1：含氮量高的天然气液化及氦气回收实例
预处理后的原料气气质组成及工况条件：
原料气处理规模：30×104m3/d
原料气压力：5MPa
原料气温度：40℃
原料气组成见表1。
表1、原料气组成
天然气组分 H<sub>2</sub> He N<sub>2</sub> C<sub>1</sub> C<sub>2</sub> C<sub>3</sub> iC<sub>4</sub> nC<sub>4</sub> nC<sub>5</sub> C<sub>6</sub>
天然气组成，mol％ 0.0011 0.35000 9.0000 90.3498 0.2298 0.0199 0.0443 0.004 0.0008 0.0003
本发明提供的天然气液化及氦气回收实施例1工艺流程如图1所示，其流程简述如下：
(1)原料气经预处理(脱碳脱水等)进入预冷器(E-101)、主冷箱(E-102)降温至-85.8℃，进入重烃分离器进行气液分离，重烃分离器液相预冷原料气后去外输，重烃分离器气相再经主冷箱(E-102)降温至-150℃，节流降压至350kPa后进入闪蒸罐(V-102)。
(2)闪蒸罐(V-102)液相增压至600kPa后去脱氮塔(T-101)进行脱氮。闪蒸罐(V-102)气相经过压缩机(K-101)增压至4MPa后在主冷箱和氦回收冷箱降温至-155℃后进入氦回收塔(T-102)中部进行氦回收。
(3)氦气回收塔(T-102)塔顶气相被集成在塔顶的冷凝器(E-104)冷凝，冷凝后气相作为粗氦产品在氦回收冷箱内复热后作为粗氦产品，氦气回收塔液相分为两股物流，第一股(30.97mol％)在氦回收冷箱内换热升温至-118℃左右后自氦气回收塔塔底进料，第二股液相(69.03mol％)作为脱氮塔第二股进料。
(4)脱氮塔(T-101)塔顶气相为高纯氮气，在主冷箱复热至-100℃后进入增压单元，脱氮塔塔底液相分为两股，第一股(13.83mol％)液相在主冷箱内升温至-137℃后自脱氮塔塔底进料。第二股(86.17mol％)在氦回收冷箱(E-103)降温至-160℃后节流至120kPa进入LNG储罐。
(5)制冷循环采用混合冷剂制冷和高纯度氮气制冷循环，混合冷剂提供中压液相和高压气相两股冷剂，中压液相混合冷剂在主冷箱(E-102)内降温至-20℃，高压气相混合冷剂在主冷箱降温至-160℃后，节流至380kPa为主冷箱提供冷量，复热-26℃后与降温节流后的原中压冷剂混合为主冷箱提供冷量；高纯度氮气冷剂(3000kPa)分为两股，分别和第一股(11.25mol％)在主冷箱降温至-150℃并节流至400kPa后为脱氮塔顶提供冷量，第二股(88.75mol％)在氦回收冷箱降温至-175℃并节流至450kPa后为氦气回收塔塔顶冷凝器(E-104)提供冷量。
天然气液化及氦气回收流程主要参数表2、表3，模拟结果表明：流程总压缩功为3855kW，主要包括自于混合冷剂制冷循环压缩功和高纯度氮气制冷循环压缩功。氦气回收率为95.76％，粗氦产品纯度为70.69％。
表2天然气液化及氦气回收流程主要参数
Figure GDA0003636552190000041
Figure GDA0003636552190000051
表3粗氦产品、LNG气质组成及工况条件
Figure GDA0003636552190000052
实例2：含氮量低的天然气液化及氦气回收实例
预处理后的原料气气质组成及工况条件：
原料气处理规模：30×104m3/d
原料气压力：4.5MPa
原料气温度：40℃
原料气组成见表4。
表4原料气组成
天然气组分 H<sub>2</sub> He N<sub>2</sub> C<sub>1</sub> C<sub>2</sub> C<sub>3</sub> iC<sub>4</sub> nC<sub>4</sub> nC<sub>5</sub> C<sub>6</sub>
天然气组成，mol％ 0.0011 0.3000 2.0000 97.3998 0.2298 0.0199 0.0443 0.004 0.0008 0.0003
本发明提供的天然气液化及氦气回收方法实施例2工艺流程如图2所示，其流程简述如下：
(1)原料气经预处理(脱碳脱水等)进入预冷器(E-101)、主冷箱(E-102)降温至-84.3℃，进入重烃分离器进行气液分离，重烃分离器液相预冷原料气后去外输，重烃分离器气相再经主冷箱(E-102)降温至-152℃，节流降压至150kPa后进入闪蒸罐(V-102)。
(2)闪蒸罐(V-102)液相增压至600kPa后在主冷箱(E-102)降温至-160℃后节流至120kPa进入LNG储罐。
(3)闪蒸罐(V-102)气相经过压缩机(K-101)增压至4MPa后在主冷箱和氦回收冷箱降温至-143℃后进入氦气回收塔(T-102)中部进行氦气回收，氦气回收塔塔顶部分气相被集成在塔顶的冷凝器(E-104)冷凝回流，氦气回收塔塔顶气相作为粗氦产品在氦回收冷箱内复热后作为粗氦产品，氦气回收塔塔底液相分为两股物流，第一股(33.34mol％)在氦回收冷箱内换热升温至-100℃左右后自氦气回收塔塔底进料，第二股液相(66.66mol％)节流至500kPa后在氦回收冷箱中复热至-114℃，再经主冷箱降温至-150℃后，节流至120kPa进入闪蒸罐(V-103)，闪蒸罐液相进入LNG储罐，闪蒸罐气相混入BOG。
(4)制冷循环采用混合冷剂制冷和高纯度氮气制冷，混合冷剂提供中压液相和高压气相两股冷剂，中压液相混合冷剂在主冷箱(E-102)内降温至-20℃，高压气相混合冷剂依次在主冷箱降温至-160℃，节流至350kPa为主冷箱提供冷量后，复热-26℃后与降温节流后的中压冷剂混合为主冷箱提供冷量；高纯度氮气冷剂(3000kPa)为氦回收冷箱提供冷量，降温至-177℃后，节流至450kPa后为氦回收塔顶提供冷量后，进入氦回收冷箱复热至-114℃后进入高纯度氮气增压系统。
天然气液化及氦气回收流程主要参数表5、表6，模拟结果表明：流程总压缩功为3629kW。氦气回收率为98.67％，粗氦产品浓度为70.71％。
表5天然气液化及氦气回收流程主要参数
项目 工艺参数
天然气处理规模，10<sup>4</sup>m<sup>3</sup>/d 30×10<sup>4</sup>
原料气压力，MPa 4.5
原料气温度，℃ 40
氦气回收率，％ 98.67
氦气纯度，％ 70.71
混合冷剂制冷循环压缩功，kW 3544
氮气制冷循环压缩功，kW 19
低温分离器气相增压压缩功，kW 66
总压缩功，kW 3629
表6粗氦产品、LNG气质组成及工况条件
Figure GDA0003636552190000061
Figure GDA0003636552190000071

Claims (10)

1.一种天然气液化及氦气回收方法，其特征在于，包括以下步骤：
(1)净化处理后的原料气经预冷器(E-101)预冷后，经主冷箱(E-102)降温重烃分离器(V-101)进行气液分离，重烃分离器液相预冷原料气后去外输气，重烃分离器气相进入主冷箱(E-102)进一步降温后，节流进入闪蒸罐(V-102)；
(2)闪蒸罐(V-102)液相经泵(P-101)增压后进入脱氮塔(T-101)中部进行脱氮，脱氮塔塔顶气相为高纯氮气，在主冷箱复热后进入氮气增压单元，脱氮塔塔底液相分为两股，一股在主冷箱降温后节流进入LNG储罐，另一股液相在主冷箱内复热后自脱氮塔塔底进料；
(3)闪蒸罐(V-102)气相经过压缩机(K-101)增压后在主冷箱和氦回收冷箱降温后进入氦气回收塔(T-102)中部进行氦回收，氦气回收塔塔顶设置集成的冷凝器(E-104)，氦气回收塔气相经氦回收冷箱(E-103)复热后作为粗氦产品，氦气回收塔液相部分在氦回收冷箱内换热升温后自氦气回收塔塔底进料，另一股液相先节流膨胀为氦回收冷箱提供热量后在主冷箱(E-102)中降温进入脱氮塔上部；
(4)制冷循环采用混合冷剂制冷和氮气制冷，混合冷剂经过增压后提供两股冷剂进入主冷箱降温，高压气相冷剂在主冷箱降温后节流为主冷箱提供冷量，中压液相冷剂在主冷箱内降温后节流后与复热后的原高压气相冷剂混合后为主冷箱提供冷量，氮气冷剂提供两股冷剂，一股经过主冷箱降温后节流后为脱氮塔顶提供冷量，另一股经过主冷箱和氦回收冷箱降温后节流后为氦回收冷箱和氦气回收塔顶提供冷量，脱氮塔顶气相经主冷箱(E-102)复热后与经氦回收冷箱复热后的高纯度氮气冷剂混合经压缩机增压后完成制冷循环。
2.如权利要求1所述的一种天然气液化及氦气回收方法，其特征在于，原料气经过预冷器(E-101)预冷后，经主冷箱(E-102)降温后重烃分离器(V-101)，重烃分离器(V-101)气相经压缩机增压后在主冷箱(E-102)进一步降温后进入闪蒸罐(V-102)，重烃分离器(V-101)液相重烃去外输气。
3.如权利要求1所述的一种天然气液化及氦气回收方法，其特征在于，闪蒸罐(V-102)液相经泵增压后进入脱氮塔中部进行脱氮，闪蒸罐气相经压缩机增压后在主冷箱、氦回收冷箱降温后进入氦气回收塔。
4.如权利要求1所述的一种天然气液化及氦气回收方法，其特征在于，氦气回收塔塔底物流分为两股，第一股作为氦气回收塔回流在氦回收冷箱内复热后自塔底进料，第二股经调压后进入脱氮塔上部。
5.如权利要求1所述的一种天然气液化及氦气回收方法，其特征在于，脱氮塔塔底物流分为两股，第一股在主冷箱内复热后自脱氮塔塔底进料，第二股在主冷箱内降温后调压进入LNG储罐。
6.如权利要求1所述的一种天然气液化及氦气回收方法，其特征在于，当原料气中氮气的摩尔百分数含量低于3％时，取消脱氮塔，闪蒸罐(V-102)液相在主冷箱内降温后节流降压直接进入LNG储罐，氦气回收塔塔底出料经节流膨胀提供冷量后在主冷箱中降温后在闪蒸罐(V-103)中闪蒸后进入LNG储罐。
7.如权利要求1所述的一种天然气液化及氦气回收方法，其特征在于，所述主冷箱(E-102)均采用多股板翅式换热器，将八股热流与三股冷流集成在主冷箱中，主冷箱的八股热流分别为原料气、混合冷剂制冷循环2股、高纯度氮气制冷循环1股、重烃分离器(V-101)气相物流、闪蒸罐(V-102)气相增压物流、脱氮塔塔底其中一股凝液、氦气回收塔复热凝液；主冷箱的三股冷流分别为混合冷剂制冷循坏、高纯氮气产品物流，脱氮塔塔底另一股凝液。
8.如权利要求1所述的一种天然气液化及氦气回收方法，其特征在于，所述氦回收冷箱(E-103)采用多股板翅式换热器，将两股热流与四股冷流分别集成于氦回收冷箱(E-103)中；氦回收冷箱的两股热流为原料气物流、高纯氮气制冷循环1股；四股冷流分别为高纯氮气制冷循环1股、粗氦产品物流、氦气回收塔底出料物流2股。
9.如权利要求1所述的一种天然气液化及氦气回收方法，其特征在于，制冷循环采用混合冷剂制冷和高纯度氮气制冷联合制冷方法，混合冷剂主要为天然气液化和高纯度氮气制冷循环提供冷量，高纯度氮气制冷循环分别为天然气脱氮塔和氦回收塔提供冷量。
10.如权利要求1所述的一种天然气液化及氦气回收方法，其特征在于，所述原料气经过净化预处理，保证流程中天然气不形成二氧化碳固体和天然气水合物，可适应于原料气中戊烷及戊烷以上的重烃含量高于70mg/m3，或原料气中芳香烃摩尔含量高于10-6的情况。
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