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CN116891214A - Low-energy-consumption low-carbon hydrocarbon steam reforming hydrogen production system and method - Google Patents

Low-energy-consumption low-carbon hydrocarbon steam reforming hydrogen production system and method Download PDF

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CN116891214A
CN116891214A CN202310765806.9A CN202310765806A CN116891214A CN 116891214 A CN116891214 A CN 116891214A CN 202310765806 A CN202310765806 A CN 202310765806A CN 116891214 A CN116891214 A CN 116891214A
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李国庆
王萍平
王浩然
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South China University of Technology SCUT
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Abstract

本发明属于石油化工技术领域,公开了一种低能耗的低碳烃水蒸汽重整制氢系统及方法。本发明的工艺通过合理巧妙地设计系统的管路、改用增压泵、增设透平~供电系统和换热器,以及增加低碳烃压力与原料反应制氢的反应压力,不仅实现提高炼厂产生液态低碳烃和系统中的能源的综合利用率,而且能够实现不同状态的原料进料、低耗能、低成本地制得高纯度的产品氢。同时,本发明还提供了一种基于现有天然气制氢系统的、管路改动少的、低耗能的、与工艺匹配程度高的系统,特别适合规模化氢气生产与液态低碳烃的回收利用。

The invention belongs to the technical field of petrochemical industry and discloses a low-energy consumption low-carbon hydrocarbon steam reforming hydrogen production system and method. The process of the present invention not only improves the refining process by rationally and skillfully designing the pipeline of the system, switching to a booster pump, adding a turbine-power supply system and a heat exchanger, and increasing the pressure of low-carbon hydrocarbons and the reaction pressure of reacting raw materials with hydrogen. The plant produces liquid low-carbon hydrocarbons and comprehensive utilization of energy in the system, and can realize the feeding of raw materials in different states, low energy consumption, and low-cost production of high-purity product hydrogen. At the same time, the present invention also provides a system based on the existing natural gas hydrogen production system with few pipeline changes, low energy consumption, and high degree of matching with the process. It is particularly suitable for large-scale hydrogen production and recovery of liquid low-carbon hydrocarbons. use.

Description

一种低能耗的低碳烃水蒸汽重整制氢系统及方法A low-energy consumption low-carbon hydrocarbon steam reforming hydrogen production system and method

技术领域Technical Field

本发明属于石油化工技术领域,具体涉及一种低能耗的低碳烃水蒸汽重整制氢系统及方法。The invention belongs to the technical field of petrochemical industry, and in particular relates to a low-energy consumption low-carbon hydrocarbon steam reforming hydrogen production system and method.

背景技术Background Art

随着裂化工艺(Cracking Process,CP)的普及,炼油工业中C3、C4低碳烷烃烃产量增加,丙烷、丁烷相对过剩,部分炼厂将其作为燃料直接燃烧,造成能源高质低用,故炼厂产生的液态低碳烃(碳原子数目≤6)副产品难以得到有效率回收与利用的问题。烷烃脱氢技术(Paraffin Dehydrogenation,PDH)是通过催化脱氢将低碳烷烃转化为高附加值烯烃,但目的产物烯烃选择性较低,且投资大、能耗高,仅适用于大型炼厂,小型炼厂难以实施。With the popularization of the cracking process (CP), the production of C 3 and C 4 low-carbon alkanes in the oil refining industry has increased, and propane and butane are relatively in excess. Some refineries directly burn them as fuel, resulting in high-quality and low-use energy. Therefore, the liquid low-carbon hydrocarbons (carbon number ≤ 6) produced by the refinery are difficult to be efficiently recovered and utilized. Paraffin dehydrogenation (PDH) technology converts low-carbon alkanes into high-value-added olefins through catalytic dehydrogenation, but the target product olefin selectivity is low, and the investment is large and the energy consumption is high. It is only applicable to large refineries and difficult to implement in small refineries.

氢气作为化学和能源产品,被广泛应用于炼油、化工、新能源等工业领域。一般来说,液态低碳烃如果要进行催化重整制氢气反应的话,为了提高反应效率、原料的利用率和氢气的转化率,那么就需要消耗能量将其预先转化为气态的反应物再进行反应。As a chemical and energy product, hydrogen is widely used in industrial fields such as oil refining, chemical industry, and new energy. Generally speaking, if liquid low-carbon hydrocarbons are to be catalytically reformed to produce hydrogen, in order to improve the reaction efficiency, the utilization rate of raw materials, and the conversion rate of hydrogen, it is necessary to consume energy to convert them into gaseous reactants before the reaction.

基于此原因,目前炼油厂制氢大多采用天然气或含有甲烷的炼厂气蒸汽重整工艺(Steam Reforming,SR)。现有技术以甲烷作为原料气,在高温和催化剂作用下与水蒸汽反应生产氢气,一般反应压力需要3.0MPa~4.0MPa,故原料气增压功耗大,并且反应后约800℃~900℃的转化气仅由余热锅炉产蒸汽回收热量。但是,这种工艺不仅存在余热锅炉换热端面温差较大导致传热损高的缺陷,还存在整体过程压力能未得到有效回收,导致制氢过程能量回收过程效率较低的技术问题。此外,还考虑到部分地区天然气匮乏,需外购液化天然气做制氢原料,储存、运输成本较高的问题。For this reason, most refineries currently use steam reforming (SR) of natural gas or refinery gas containing methane to produce hydrogen. The existing technology uses methane as the raw gas, which reacts with water vapor under high temperature and catalyst to produce hydrogen. The general reaction pressure requires 3.0MPa~4.0MPa, so the raw gas pressurization power consumption is large, and the conversion gas at about 800℃~900℃ after the reaction is only recovered by the waste heat boiler to produce steam. However, this process not only has the problem of large temperature difference at the heat exchange end of the waste heat boiler, but also leads to heat transfer problems. The defects of high loss and the fact that the overall process pressure energy is not effectively recovered, resulting in low efficiency of energy recovery process in hydrogen production. In addition, considering the shortage of natural gas in some areas, it is necessary to purchase liquefied natural gas as raw material for hydrogen production, and the high storage and transportation costs.

因此,亟需开发一种不仅对现有系统改动少,而且能够有效利用液态低碳烃,还具备低耗能、产品纯度高、低成本的催化重整制氢的方法。Therefore, there is an urgent need to develop a method for producing hydrogen through catalytic reforming that not only requires little modification to the existing system, but can effectively utilize liquid low-carbon hydrocarbons and has low energy consumption, high product purity and low cost.

发明内容Summary of the invention

针对天然气/炼厂气水蒸汽重整制氢工艺原料气压缩机能耗高、转化气余热只产蒸汽导致第二定律能效低,并且部分炼油厂丙烷、丁烷相对过剩的问题。同时,为了克服现有技术存在的能量回收利用率低、液态低碳烃利用率低、催化制氢能耗大等问题,本发明的目的之一在于提供一种低能耗的低碳烃水蒸汽重整制氢的方法。In view of the high energy consumption of the raw gas compressor in the natural gas/refinery gas steam reforming hydrogen production process, the waste heat of the reformed gas only produces steam, resulting in low second law energy efficiency, and the relative excess of propane and butane in some refineries. At the same time, in order to overcome the problems of low energy recovery utilization rate, low utilization rate of liquid low-carbon hydrocarbons, and high energy consumption of catalytic hydrogen production in the prior art, one of the purposes of the present invention is to provide a low-energy consumption method for hydrogen production by steam reforming of low-carbon hydrocarbons.

本发明的目的之二在于提供一种低能耗的低碳烃水蒸汽重整制氢系统。A second object of the present invention is to provide a low-energy consumption low-carbon hydrocarbon steam reforming hydrogen production system.

本发明的关键/发明构思:本发明的关键在于提高能量回收效率,降低制氢原料成本。本发明通过合理巧妙地设计系统的管路与设备,以及增加低碳烃(液态)原料压力以提高制氢过程的反应压力,既实现提高原料的流量,提高系统中的热能与内能的综合利用,又能够实现液态原料进料、低耗能地制得高纯度的产品氢。Key points of the invention/inventive concept: The key points of the invention are to improve the energy recovery efficiency and reduce the cost of hydrogen production raw materials. The invention increases the flow rate of raw materials and the comprehensive utilization of heat energy and internal energy in the system by rationally and cleverly designing the system's pipelines and equipment, and increasing the pressure of low-carbon hydrocarbon (liquid) raw materials to increase the reaction pressure of the hydrogen production process, thereby achieving both increased raw material flow and improved comprehensive utilization of heat energy and internal energy in the system, and achieving liquid raw material feeding and low-energy consumption to produce high-purity product hydrogen.

为了实现上述目的,本发明所采取的技术方案是:In order to achieve the above object, the technical solution adopted by the present invention is:

第一方面,本发明提供一种低能耗的低碳烃水蒸汽重整制氢的方法,包括以下步骤:In a first aspect, the present invention provides a method for producing hydrogen by steam reforming of low-carbon hydrocarbons with low energy consumption, comprising the following steps:

原料增压至3.5~5.5MPa,预加热和多级加热至340~380℃后,再与中压蒸汽混合,在转化炉进行催化重整制氢反应,得到转化气;The raw material is pressurized to 3.5-5.5 MPa, preheated and multi-stage heated to 340-380°C, and then mixed with medium-pressure steam to undergo catalytic reforming and hydrogen production reaction in the reformer to obtain reformed gas;

转化气经透平膨胀过程和余热锅炉回收内能和热量,在390~420℃进行中温变换反应、冷却,得到变换气;部分所述变换气作为热源用于所述预加热后,再经冷却、变压吸附,得到产品氢和解吸气;The conversion gas is subjected to a turbine expansion process and a waste heat boiler to recover internal energy and heat, and is subjected to a medium-temperature conversion reaction at 390-420°C and cooling to obtain conversion gas; a portion of the conversion gas is used as a heat source for the preheating, and then subjected to cooling and pressure swing adsorption to obtain product hydrogen and desorbed gas;

其中,所述催化重整制氢反应的反应条件如下:反应压力为3.0~4.8MPa,反应温度为800~900℃;所述转化炉的热源来源于所述解吸气、补充燃料和空气燃烧反应产生的热量。The reaction conditions of the catalytic reforming hydrogen production reaction are as follows: the reaction pressure is 3.0-4.8 MPa, and the reaction temperature is 800-900°C; the heat source of the converter comes from the heat generated by the combustion reaction of the desorbed gas, supplementary fuel and air.

具体地,所述中温变换反应为进一步产生氢气,并发生一氧化碳转化为二氧化碳的反应;所述工艺回收变换气的余热用于加热,有效减少了原料预热的饱和蒸汽的消耗,有效提高饱和蒸汽的利用率,同时还降低了变换气的冷却负荷。Specifically, the medium-temperature shift reaction further produces hydrogen and converts carbon monoxide into carbon dioxide; the process recovers the waste heat of the shift gas for heating, effectively reducing the consumption of saturated steam for preheating the raw materials, effectively improving the utilization rate of saturated steam, and also reducing the cooling load of the shift gas.

在一些实施方式中,所述低能耗的低碳烃水蒸汽重整制氢的方法,包括以下步骤:In some embodiments, the method for producing hydrogen by steam reforming of low-carbon hydrocarbons with low energy consumption comprises the following steps:

1)原料增压至3.5~5.5MPa,预加热和多级加热至340~380℃,脱硫处理,与中压蒸汽混合后,再在转化炉进行催化重整制氢反应,得到转化气;1) The raw material is pressurized to 3.5-5.5 MPa, preheated and multi-stage heated to 340-380°C, desulfurized, mixed with medium-pressure steam, and then catalytically reformed in a reformer to produce hydrogen to obtain reformed gas;

2)转化气利用透平膨胀过程回收内能、余热锅炉回收热量和产汽,在390~420℃进行中温变换反应、冷却,得到一级变换气;所述一级变换气经一级冷却、二级冷却,得到122~132℃二级变换气;2) The conversion gas utilizes the turbine expansion process to recover internal energy, the waste heat boiler to recover heat and produce steam, and undergoes a medium-temperature conversion reaction at 390-420°C and cooling to obtain a primary conversion gas; the primary conversion gas undergoes primary cooling and secondary cooling to obtain a secondary conversion gas at 122-132°C;

3)将步骤2)所述二级变换气作为热源用于步骤1)所述预加热后,再经冷却、变压吸附,得到产品氢和解吸气;3) using the secondary shift gas in step 2) as a heat source for the preheating in step 1), followed by cooling and pressure swing adsorption to obtain product hydrogen and desorbed gas;

其中,步骤1)所述中压蒸汽的压力为4.0~5.0MPa、温度为380~430℃;Wherein, the medium-pressure steam in step 1) has a pressure of 4.0-5.0 MPa and a temperature of 380-430° C.;

步骤1)所述催化重整制氢反应的反应条件如下:反应压力为3.0~4.8MPa,反应温度为800~900℃;步骤1)所述转化炉的热源来源于步骤3)所述解吸气、补充燃料和空气燃烧反应产生的热量。The reaction conditions of the catalytic reforming hydrogen production reaction in step 1) are as follows: the reaction pressure is 3.0-4.8 MPa, and the reaction temperature is 800-900°C; the heat source of the reformer in step 1) comes from the heat generated by the combustion reaction of the desorbed gas, supplementary fuel and air in step 3).

在一些实施方式中,步骤1)所述原料增压至4.0~5.3MPa。In some embodiments, the raw material in step 1) is pressurized to 4.0-5.3 MPa.

在一些实施方式中,步骤1)还包括将脱硫处理后的原料被转化炉预热至410~430℃,与中压蒸汽混合后用转化炉预热至580~630℃后,再在转化炉的炉管进行催化重整制氢反应。In some embodiments, step 1) further includes preheating the desulfurized raw material to 410-430° C. in a converter, mixing with medium-pressure steam, and then preheating the raw material to 580-630° C. in a converter, and then performing catalytic reforming to produce hydrogen in the converter tubes.

在一些实施方式中,步骤1)所述原料包括液态的丙烷、液态的丁烷、液态的戊烷中的至少一种。In some embodiments, the raw material in step 1) includes at least one of liquid propane, liquid butane, and liquid pentane.

在一些实施方式中,步骤1)所述原料包括液态丙烷;且液态丙烷的含量为95%~99%(体积分数)。In some embodiments, the raw material in step 1) includes liquid propane; and the content of liquid propane is 95% to 99% (volume fraction).

在一些实施方式中,步骤1)所述原料还包括气态烷烃。具体地,所述气态烷烃选自甲烷、乙烷、丙烷、丁烷和戊烷中的至少一种。In some embodiments, the raw material in step 1) further comprises gaseous alkanes. Specifically, the gaseous alkanes are selected from at least one of methane, ethane, propane, butane and pentane.

在一些实施方式中,步骤1)所述液态的原料的来源为气体储罐、炼油厂、炼气厂中的一种或多种。In some embodiments, the source of the liquid raw material in step 1) is one or more of a gas storage tank, an oil refinery, and a gas refinery.

具体地,液态的丙烷等低碳烷烃是常见的炼油厂和炼气厂的原有产生的液态低碳烃副产品;具有碳氢比高,是优质的制氢原料;兼具能源密度高的特性。基于以上特点,本发明能够通过设计控制反应压力和简单改进现有系统,从而提出一种低能耗的低碳烃水蒸汽重整制氢的方法,并集成透平和余热锅炉回收转化气压力能及热能,提高能量回收效率。Specifically, liquid propane and other low-carbon alkanes are common liquid low-carbon hydrocarbon byproducts originally produced by oil refineries and gas refineries; they have a high carbon-to-hydrogen ratio and are high-quality hydrogen production raw materials; they also have the characteristics of high energy density. Based on the above characteristics, the present invention can design and control the reaction pressure and simply improve the existing system, thereby proposing a low-energy consumption method for producing hydrogen by steam reforming of low-carbon hydrocarbons, and integrating turbines and waste heat boilers to recover the pressure energy and thermal energy of the converted gas, thereby improving the energy recovery efficiency.

在一些实施方式中,步骤1)所述原料的压力为1.0MPa~1.8MPa。In some embodiments, the pressure of the raw material in step 1) is 1.0 MPa to 1.8 MPa.

在一些更优选的实施方式中,步骤1)所述原料的参数如下:In some more preferred embodiments, the parameters of the raw materials in step 1) are as follows:

主要成分:液态丙烷,液态丙烷的含量:95%~99%(体积分数),温度:20~40℃,压力:1.4~1.6MPa。Main component: liquid propane, liquid propane content: 95% to 99% (volume fraction), temperature: 20 to 40°C, pressure: 1.4 to 1.6 MPa.

在一些实施方式中,步骤1)所述原料的流量为10~30t/h。In some embodiments, the flow rate of the raw material in step 1) is 10 to 30 t/h.

在一些优选的实施方式中,步骤1)所述原料的流量为12~18t/h。In some preferred embodiments, the flow rate of the raw material in step 1) is 12 to 18 t/h.

在一些实施方式中,步骤1)所述转化气的压力为3.2~4.8MPa。In some embodiments, the pressure of the conversion gas in step 1) is 3.2-4.8 MPa.

在一些实施方式中,所述余热锅炉的入口处的转化气的压力为2.6~3.2MPa。In some embodiments, the pressure of the reformed gas at the inlet of the waste heat boiler is 2.6-3.2 MPa.

在一些实施方式中,所述余热锅炉的入口处的转化气的温度为770~840℃。In some embodiments, the temperature of the reformed gas at the inlet of the waste heat boiler is 770-840°C.

在一些实施方式中,步骤1)所述催化重整制氢反应的催化剂为Z417、Z418中的一种或多种。具体地,Z417、Z418均为镍基催化剂。In some embodiments, the catalyst for the catalytic reforming hydrogen production reaction in step 1) is one or more of Z417 and Z418. Specifically, Z417 and Z418 are both nickel-based catalysts.

在一些实施方式中,步骤1)所述中压蒸汽的流量为52~68t/h。In some embodiments, the flow rate of the medium-pressure steam in step 1) is 52-68 t/h.

在一些实施方式中,步骤1)所述催化重整制氢反应的使用的蒸汽流量为52~68t/h。In some embodiments, the steam flow rate used in the catalytic reforming hydrogen production reaction in step 1) is 52-68 t/h.

在一些实施方式中,步骤1)所述催化重整制氢反应的蒸汽碳比为2.8~3.8。In some embodiments, the steam-to-carbon ratio of the catalytic reforming hydrogen production reaction in step 1) is 2.8 to 3.8.

在一些优选的实施方式中,步骤1)所述催化重整制氢反应的蒸汽碳比为3.0~3.5。In some preferred embodiments, the steam-to-carbon ratio of the catalytic reforming hydrogen production reaction in step 1) is 3.0 to 3.5.

具体地,所述蒸汽碳具体指的是水蒸汽与原料中碳原子的摩尔流量之比。Specifically, the steam carbon specifically refers to the ratio of the molar flow rate of water vapor to the carbon atoms in the feedstock.

在一些实施方式中,步骤1)所述转化气中的氢气含量为65%~73%(体积分数,干基),CO含量为13%~15%(体积分数,干基)。In some embodiments, the hydrogen content in the conversion gas in step 1) is 65% to 73% (volume fraction, dry basis), and the CO content is 13% to 15% (volume fraction, dry basis).

在一些实施方式中,步骤1)所述中压蒸汽的制备过程包括:In some embodiments, the process for preparing the medium-pressure steam in step 1) comprises:

将步骤2)所述冷却、一级冷却和二级冷却产生的工艺冷凝水通入酸性水汽提塔的中部;将步骤3)所述冷却产生的工艺冷凝水通入在酸性水汽提塔的顶部;并在酸性水汽提塔的底部通入加热蒸汽,分离出酸性气体和纯净水;The process condensed water generated by the cooling, primary cooling and secondary cooling in step 2) is introduced into the middle of the acidic water stripping tower; the process condensed water generated by the cooling in step 3) is introduced into the top of the acidic water stripping tower; and heating steam is introduced into the bottom of the acidic water stripping tower to separate acidic gas and pure water;

除盐水加热至100~112℃,与一部分纯净水(即回用纯净水)混合(实现原料水的收集与除氧),经加压,除氧水换热器、余热锅炉和转化炉的饱和水蒸发段加热至265~282℃,得到饱和蒸汽;所述饱和蒸汽经转化炉的蒸汽过热段进一步加热至400~450℃,得到过热蒸汽;所述部分过热蒸汽经一级原料换热器冷却得到中压蒸汽;The desalted water is heated to 100-112°C, mixed with a portion of pure water (i.e., recycled pure water) (to collect and deoxygenate the raw water), and then pressurized, and the deoxygenated water heat exchanger, waste heat boiler, and saturated water evaporation section of the converter are heated to 265-282°C to obtain saturated steam; the saturated steam is further heated to 400-450°C in the steam superheating section of the converter to obtain superheated steam; part of the superheated steam is cooled by the primary raw material heat exchanger to obtain medium-pressure steam;

其中,所述饱和蒸汽的压力为4.0~5.0MPa;所述过热蒸汽的压力为4.0~5.0MPa。Wherein, the pressure of the saturated steam is 4.0-5.0 MPa; the pressure of the superheated steam is 4.0-5.0 MPa.

在一些实施方式中,步骤1)所述多级加热步骤包括以部分饱和蒸汽为热源的一级加热和以部分过热蒸汽为热源的二级加热;剩余部分的饱和蒸汽用于被加热形成过热蒸汽;剩余部分过热蒸汽直接向外输送。具体地,对于所述饱和蒸汽来说,作为一级加热的热源和用于被加热形成过热蒸汽的流量之比为1:(18~28);优选为1:(20~26)。对于过热蒸汽来说,直接向外输送和作为二级加热的热源的流量之比1:(2.3~4.5);优选为1:(2.5~4.2)。需要说明得是:作为二级加热的热源的过热蒸汽的流量与形成中压蒸汽的流量相同。In some embodiments, the multi-stage heating step in step 1) includes primary heating using part of the saturated steam as the heat source and secondary heating using part of the superheated steam as the heat source; the remaining part of the saturated steam is used to be heated to form superheated steam; the remaining part of the superheated steam is directly transported outward. Specifically, for the saturated steam, the ratio of the flow rate as the heat source for primary heating and the flow rate used to be heated to form superheated steam is 1: (18-28); preferably 1: (20-26). For superheated steam, the ratio of the flow rate directly transported outward and the flow rate as the heat source for secondary heating is 1: (2.3-4.5); preferably 1: (2.5-4.2). It should be noted that the flow rate of the superheated steam used as the heat source for secondary heating is the same as the flow rate for forming medium-pressure steam.

在一些实施方式中,在所述中压蒸汽的制备过程中,所述饱和蒸汽的总流量为65~95t/h。In some embodiments, during the preparation of the medium-pressure steam, the total flow rate of the saturated steam is 65 to 95 t/h.

在一些实施方式中,在所述中压蒸汽的制备过程中,所述过热蒸汽的总流量为60~90t/h。In some embodiments, during the preparation of the medium-pressure steam, the total flow rate of the superheated steam is 60 to 90 t/h.

在一些实施方式中,在所述中压蒸汽的制备过程中,所述余热锅炉系统的产汽压力为4.0~5.0MPa。In some embodiments, during the preparation of the medium-pressure steam, the steam production pressure of the waste heat boiler system is 4.0-5.0 MPa.

在一些实施方式中,在所述中压蒸汽的制备过程中,所述加压具体为:将除盐水和部分所述纯净水(即回用纯净水)加压至5.2~6.6MPa,用于除氧和保证蒸汽能够输送至下个设备,最终参与催化重整制氢反应。In some embodiments, during the preparation of the medium-pressure steam, the pressurization is specifically: pressurizing the desalted water and part of the pure water (i.e., recycled pure water) to 5.2-6.6 MPa for deoxygenation and ensuring that the steam can be transported to the next equipment, and finally participate in the catalytic reforming hydrogen production reaction.

在一些实施方式中,步骤2)所述透平膨胀过程中回收的内能转化为电能,并提供给所述工艺中的设备;以实现进一步降低工艺的耗能。In some embodiments, the internal energy recovered during the turbine expansion process in step 2) is converted into electrical energy and provided to the equipment in the process, so as to further reduce the energy consumption of the process.

在一些实施方式中,步骤2)所述透平膨胀过程中的等熵效率70%~80%。优选为75%。In some embodiments, the isentropic efficiency in the turbine expansion process of step 2) is 70% to 80%, preferably 75%.

在一些实施方式中,步骤2)所述透平膨胀过程的回收能量为1000~5000kw。In some embodiments, the recovered energy of the turbine expansion process in step 2) is 1000 to 5000 kW.

在一些实施方式中,步骤3)所述冷却具体是采用空气冷却器设备,冷却至40℃。In some embodiments, the cooling in step 3) is performed using an air cooler to cool to 40°C.

在一些实施方式中,步骤3)所述产品氢和解吸气的流量之比为1:(8~9)。In some embodiments, the flow ratio of the product hydrogen and the desorption gas in step 3) is 1:(8-9).

在一些实施方式中,步骤3)所述产品氢的流量为4~6t/h。In some embodiments, the flow rate of the product hydrogen in step 3) is 4 to 6 t/h.

在一些实施方式中,步骤3)所述产品氢中的氢气(体积分数为95%~99.9%)。优选地,所述产品氢为99.9%的氢气。In some embodiments, the hydrogen in the product hydrogen of step 3) is (volume fraction is 95% to 99.9%). Preferably, the product hydrogen is 99.9% hydrogen.

在一些实施方式中,所述补充燃料的流量为0.1~2t/h。优选为0.2~0.9t/h。In some embodiments, the flow rate of the supplementary fuel is 0.1 to 2 t/h, preferably 0.2 to 0.9 t/h.

在一些实施方式中,所述补充燃料和解吸气的流量之比为(20~180):1。In some embodiments, the flow rate ratio of the supplementary fuel to the desorbed gas is (20-180):1.

在一些实施方式中,所述补充燃料为甲烷气体。In some embodiments, the supplemental fuel is methane gas.

在一些优选的实施方式中,所述空气被转化炉的低温空气预热段和高温空气预热段预热至430~450℃后,再在转化炉的燃烧室内发生所述燃烧反应。In some preferred embodiments, the air is preheated to 430-450° C. by the low-temperature air preheating section and the high-temperature air preheating section of the converter, and then the combustion reaction occurs in the combustion chamber of the converter.

在一些实施方式中,所述转化炉的空气入口温度为25℃;所述转化炉的炉管入口的温度为580~630℃;所述转化炉的炉管出口的温度为800~900℃、压力为2.84~4.64MPa;所述转化炉的排出烟气的温度为140~152℃,且排出烟气的含氧量≤3%(干基)。In some embodiments, the air inlet temperature of the converter is 25°C; the temperature of the furnace tube inlet of the converter is 580-630°C; the temperature of the furnace tube outlet of the converter is 800-900°C and the pressure is 2.84-4.64MPa; the temperature of the exhaust flue gas of the converter is 140-152°C, and the oxygen content of the exhaust flue gas is ≤3% (dry basis).

第二方面,本发明提供一种低能耗的低碳烃水蒸汽重整制氢系统包括:一级原料换热器、二级原料换热器、脱硫反应器、转化炉、余热锅炉系统、除氧水换热器、中温变换反应器、变换气第一分液罐、热水换热器、除盐水换热器、变换气第二分液罐、变换气冷却器、变换气第三分液罐、变压吸附系统和酸性水汽提塔;所述余热锅炉系统包括余热锅炉和余锅汽水分离器;所述转化炉的燃烧室设置有空气和补充燃料的入口;In a second aspect, the present invention provides a low-energy consumption low-carbon hydrocarbon steam reforming hydrogen production system comprising: a primary raw material heat exchanger, a secondary raw material heat exchanger, a desulfurization reactor, a converter, a waste heat boiler system, a deoxygenated water heat exchanger, a medium-temperature shift reactor, a first shift gas separator, a hot water heat exchanger, a desalted water heat exchanger, a second shift gas separator, a shift gas cooler, a third shift gas separator, a pressure swing adsorption system and an acidic water stripping tower; the waste heat boiler system comprises a waste heat boiler and a waste boiler steam-water separator; the combustion chamber of the converter is provided with an inlet for air and supplementary fuel;

还包括原料增压泵、预加热换热器、透平膨胀机、发电机和旁路阀;It also includes a feed booster pump, a preheating heat exchanger, a turbo expander, a generator and a bypass valve;

所述原料增压泵通过管路依次与预加热换热器、一级原料换热器、二级原料换热器、脱硫反应器、转化炉、余热锅炉、中温变换反应器、除氧水换热器、变换气第一分液罐相连;The raw material booster pump is connected to the preheating heat exchanger, the primary raw material heat exchanger, the secondary raw material heat exchanger, the desulfurization reactor, the converter, the waste heat boiler, the medium temperature shift reactor, the deoxygenated water heat exchanger, and the first shift gas separator in sequence through pipelines;

所述脱硫反应器和转化炉之间的管路上设置有接入中压蒸汽的管路;A pipeline for accessing medium-pressure steam is provided on the pipeline between the desulfurization reactor and the reformer;

所述透平膨胀机和旁路阀,以并联的形式接入转化炉和余热锅炉之间的管路,用于回收利用转化气的内能和确保系统稳定运行;The turbine expander and bypass valve are connected in parallel to the pipeline between the reformer and the waste heat boiler to recover the internal energy of the reformed gas and ensure stable operation of the system;

所述变换气第一分液罐的顶部通过管路依次与热水换热器、除盐水换热器、变换气第二分液罐相连;所述变换气第二分液罐的顶部与预加热换热器相连,再与变换气冷却器、变换气第三分液罐相连;所述变换气第三分液罐的顶部与变压吸附系统相连,且所述变压吸附系统设置有产品氢的输出管路和给转化炉提供解吸气(或燃料气)的管路;The top of the first conversion gas separator is connected to the hot water heat exchanger, the desalted water heat exchanger, and the second conversion gas separator in sequence through pipelines; the top of the second conversion gas separator is connected to the preheating heat exchanger, and then connected to the conversion gas cooler and the third conversion gas separator; the top of the third conversion gas separator is connected to the pressure swing adsorption system, and the pressure swing adsorption system is provided with an output pipeline for product hydrogen and a pipeline for providing desorption gas (or fuel gas) to the converter;

所述变换气第一分液罐的底部通过管路与变换气第二分液罐的底部相连后,再与酸性水汽提塔的中部进料口相连。The bottom of the first shift gas separator is connected to the bottom of the second shift gas separator through a pipeline, and then connected to the middle feed port of the acidic water stripping tower.

具体地,所述余热锅炉和余锅汽水分离器构成余热锅炉系统,用于回收热量与产生饱和蒸汽。由于低碳烃氢碳比高,且多为液相,故原料增压设备可用泵代替,增压能耗大幅下降;同时适当提高转化炉的操作压力,并在其出口设置透平,先回收转化气的压力能和高温热能直接做功,再通过余热锅炉回收热能产蒸汽。同时,还能够巧妙利用变换气的热能用于原料的加热。此外,在系统运行不稳定时,能够利用开启旁路阀来使得整体系统稳定,而系统稳定时,流体经过旁路阀的流量为零。Specifically, the waste heat boiler and the waste heat water separator constitute a waste heat boiler system, which is used to recover heat and generate saturated steam. Since low-carbon hydrocarbons have a high hydrogen-to-carbon ratio and are mostly in liquid phase, the raw material pressurization equipment can be replaced by a pump, and the energy consumption of pressurization is greatly reduced; at the same time, the operating pressure of the converter is appropriately increased, and a turbine is set at its outlet to first recover the pressure energy and high-temperature thermal energy of the conversion gas to directly do work, and then recover the thermal energy through the waste heat boiler to produce steam. At the same time, the thermal energy of the conversion gas can also be cleverly used for heating the raw materials. In addition, when the system is unstable, the bypass valve can be opened to stabilize the overall system, and when the system is stable, the flow rate of the fluid through the bypass valve is zero.

在一些实施方式中,所述转化炉,从低温区至高温区依次包括低温空气预热段、饱和水蒸发段、高温空气预热段、脱硫原料预热段、蒸汽过热段、转化原料预热段和辐射段;所述辐射段设置有炉管和燃烧室。In some embodiments, the converter includes, from the low-temperature zone to the high-temperature zone, a low-temperature air preheating section, a saturated water evaporation section, a high-temperature air preheating section, a desulfurization raw material preheating section, a steam superheating section, a conversion raw material preheating section and a radiation section; the radiation section is provided with furnace tubes and a combustion chamber.

在一些实施方式中,所述转化炉中的空气管路是从低温空气入口进入,经低温空气预热段、高温空气预热段与辐射段燃烧室的热空气入口相连。In some embodiments, the air pipeline in the converter enters from the low-temperature air inlet, passes through the low-temperature air preheating section, the high-temperature air preheating section, and is connected to the hot air inlet of the radiation section combustion chamber.

在一些实施方式中,所述脱硫反应器的气体出口通过管路,经转化炉的脱硫原料预热段后,与来自二级原料换热器的中压蒸汽接入管路相连;再经转化炉的蒸汽过热段与转化炉的炉管相连。In some embodiments, the gas outlet of the desulfurization reactor passes through a pipeline, passes through the desulfurization raw material preheating section of the converter, and is connected to the medium-pressure steam access pipeline from the secondary raw material heat exchanger; and then passes through the steam superheating section of the converter and is connected to the furnace tube of the converter.

在一些实施方式中,所述变换气第一分液罐的底部通过管路与变换气第二分液罐的底部相连后(用于汇集工艺冷凝水),再与酸性水汽提塔的中部进料口相连;变换气第三分液罐的底部通过管路与酸性水汽提塔的顶部进料口相连;酸性水汽提塔的底部设置有蒸汽的入口、净化水的输出的管路,且酸性水汽提塔的顶部设置有酸性气的出口。In some embodiments, the bottom of the first conversion gas separator tank is connected to the bottom of the second conversion gas separator tank through a pipeline (for collecting process condensed water), and then connected to the middle feed port of the sour water stripping tower; the bottom of the third conversion gas separator tank is connected to the top feed port of the sour water stripping tower through a pipeline; the bottom of the sour water stripping tower is provided with a steam inlet and a purified water output pipeline, and the top of the sour water stripping tower is provided with an acid gas outlet.

在一些实施方式中,所述低能耗的低碳烃水蒸汽重整制氢系统还包括:原料气压缩机、除氧器和除氧水增压泵;In some embodiments, the low-energy consumption low-carbon hydrocarbon steam reforming hydrogen production system further includes: a raw gas compressor, a deaerator, and a deoxygenated water booster pump;

除盐水换热器通过管路依次与除氧器、除氧水增压泵、除氧水换热器相连后,再与余热锅炉和余锅汽水分离器相连,用于给余锅汽水分离器提供饱和水原料。The deionized water heat exchanger is connected to the deaerator, the deionized water booster pump, and the deionized water heat exchanger in sequence through pipelines, and then connected to the waste heat boiler and the waste heat boiler steam-water separator to provide saturated water raw materials to the waste heat boiler steam-water separator.

在一些实施方式中,所述原料气压缩机和原料增压泵是以并联方式接入系统,且所述原料气压缩机与一级原料加热器相连,实现气态和液态原料混合进料。In some embodiments, the raw gas compressor and the raw material booster pump are connected to the system in parallel, and the raw gas compressor is connected to the primary raw material heater to achieve mixed feeding of gaseous and liquid raw materials.

在一些实施方式中,所述余锅汽水分离器的底部设置有经过转化炉的饱和水蒸发段的管路,用回收利用转化炉的热量制得饱和蒸汽。In some embodiments, a pipeline passing through the saturated water evaporation section of the converter is disposed at the bottom of the residual boiler steam-water separator, so as to produce saturated steam by recycling the heat of the converter.

在一些实施方式中,所述余锅汽水分离器的顶部的管路分为两路,一路经转化炉的蒸汽过热段,用于产生过热蒸汽;一路与一级原料换热器、除氧器相连,实现回收过热蒸汽中的热量并用于原料的一级加热和除氧器的加热。In some embodiments, the pipeline at the top of the residual boiler steam-water separator is divided into two routes, one route passes through the steam superheating section of the converter to generate superheated steam; the other route is connected to the primary raw material heat exchanger and the deaerator to recover the heat in the superheated steam and use it for the primary heating of the raw material and the heating of the deaerator.

在一些实施方式中,所述除氧器设置有一级原料换热器的接入管路;除氧器还设置有补充蒸汽的接入管路,用于除盐水的加热。In some embodiments, the deaerator is provided with an access pipeline for a primary raw material heat exchanger; the deaerator is also provided with an access pipeline for supplementary steam for heating the desalted water.

在一些实施方式中,经过转化炉的蒸汽过热段后的管路再分为两路,一路与直接外输的管路连接,用于过热蒸汽的外送;一路与二级原料换热器相连,用于原料的二级加热。In some embodiments, the pipeline after passing through the steam superheating section of the converter is divided into two routes, one of which is connected to the direct external transmission pipeline for the external transmission of superheated steam; and the other is connected to the secondary raw material heat exchanger for secondary heating of the raw material.

在一些实施方式中,所述酸性水汽提塔的塔底的净化水的输出的管路分为两路,一路用于直接输出,一路通过与除氧器相连,用于提供回用纯净水,并使得其与除氧水混合。In some embodiments, the output pipeline of the purified water at the bottom of the sour water stripping tower is divided into two routes, one for direct output and the other connected to the deaerator to provide recycled pure water and mix it with deoxygenated water.

在一些实施方式中,所述透平膨胀机还通过导线和发电机相连,以此实现转化气的内能向机械能、电能转化,以及提高系统中的转化气的内能利用率。In some embodiments, the turbo expander is also connected to a generator via a conductor, so as to achieve the conversion of the internal energy of the conversion gas into mechanical energy and electrical energy, and improve the internal energy utilization rate of the conversion gas in the system.

在一些实施方式中,所述发电机通过导线与增压设备相连,用于给系统提供电能。具体地,所述增压设备为原料气压缩机、原料增压泵、除氧水增压泵中的至少一种。In some embodiments, the generator is connected to a boosting device via a wire to provide electrical energy to the system. Specifically, the boosting device is at least one of a raw gas compressor, a raw material boosting pump, and a deoxygenated water boosting pump.

在一些实施方式中,所述热水换热器设置有取热介质的接入口。所述取热介质为65-75℃的热水。In some embodiments, the hot water heat exchanger is provided with an inlet for a heat medium, and the heat medium is hot water at 65-75°C.

在一些实施方式中,所述变压吸附系统包括吸附器、缓冲罐、程序控制阀、调节阀及管线等设备。In some embodiments, the pressure swing adsorption system includes an adsorber, a buffer tank, a program control valve, a regulating valve, a pipeline and other equipment.

本发明的有益效果是:本发明提供了一种不仅能够满足不同状态的原料进料条件,而且能够有效利用液态低碳烃,耗能低、产品氢纯度高、成本低的催化重整制氢的工艺。同时,本发明还提供了一种与上述工艺匹配的、对现有系统改动少、低耗能、产品纯度高、原料利用率高的催化重整制氢的系统。The beneficial effects of the present invention are as follows: the present invention provides a process for producing hydrogen by catalytic reforming that can not only meet the conditions for raw material feeding in different states, but also effectively utilize liquid low-carbon hydrocarbons, with low energy consumption, high product hydrogen purity, and low cost. At the same time, the present invention also provides a system for producing hydrogen by catalytic reforming that matches the above process, has little modification to the existing system, low energy consumption, high product purity, and high raw material utilization.

具体为:Specifically:

(1)本发明丰富了炼厂液态丙烷、液态丁烷等低碳烃的应用途径,特别为天然气供应受限的炼厂提供新的高碳氢比优质制氢原料;(1) The present invention enriches the application of low-carbon hydrocarbons such as liquid propane and liquid butane in refineries, and especially provides new high-carbon-to-hydrogen ratio high-quality hydrogen production raw materials for refineries with limited natural gas supply;

(2)本发明原料增压设备为泵,能有效用于液态低碳烃,原料增压功耗大幅降低;(2) The raw material pressurizing equipment of the present invention is a pump, which can be effectively used for liquid low-carbon hydrocarbons, and the power consumption of raw material pressurizing is greatly reduced;

(3)本发明通过回收变换气余热汽化液相原料,减少了原料预热蒸汽消耗,同时降低了变换气的冷却负荷;(3) The present invention recovers the waste heat of the conversion gas to vaporize the liquid raw material, thereby reducing the consumption of raw material preheating steam and reducing the cooling load of the conversion gas;

(4)本发明通过增设转化炉出口气体膨胀透平,大大提高了转化气的热力学第二定律能效。现有技术中的转化气温度860℃,而所产3.5MPag(表压,即3.5MPa)中压蒸汽的饱和温度仅有244℃,产汽过程的传热温差为616℃,是典型的高能低用。经透平做功后,转化气温度大幅降低,从而降低产汽过程的传热温差,既能保证中压反应器操作,又大大提高了转化气能效。虽然透平做功输出能量会减少中压蒸汽的产量,但以电换汽,是等值的能量升级。(4) The present invention greatly improves the energy efficiency of the conversion gas according to the second law of thermodynamics by adding a gas expansion turbine at the outlet of the conversion furnace. The temperature of the conversion gas in the prior art is 860°C, while the saturation temperature of the produced 3.5MPag (gauge pressure, i.e. 3.5MPa) medium-pressure steam is only 244°C, and the heat transfer temperature difference in the steam production process is 616°C, which is a typical high-energy and low-use. After the turbine does work, the temperature of the conversion gas is greatly reduced, thereby reducing the heat transfer temperature difference in the steam production process, which can not only ensure the operation of the medium-pressure reactor, but also greatly improve the energy efficiency of the conversion gas. Although the output energy of the turbine work will reduce the output of medium-pressure steam, exchanging electricity for steam is an equivalent energy upgrade.

(5)本发明设置膨胀透平旁路,保证了工艺的稳定性;(5) The present invention provides an expansion turbine bypass to ensure process stability;

(6)本发明不仅适用于天然气/甲烷制氢的系统改造,而且能够降低系统的能耗和生产成本。(6) The present invention is not only applicable to the system transformation of natural gas/methane hydrogen production, but also can reduce the energy consumption and production cost of the system.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1为本发明对比例中的低碳烃水蒸汽重整制氢系统的结构示意图。FIG1 is a schematic diagram of the structure of a low-carbon hydrocarbon steam reforming hydrogen production system in a comparative example of the present invention.

图2为本发明实施例中的改进后的低耗能低碳烃水蒸汽重整制氢系统的结构示意图。FIG2 is a schematic structural diagram of an improved low-energy low-carbon hydrocarbon steam reforming hydrogen production system in an embodiment of the present invention.

图3为本发明中的低碳烃水蒸汽重整制氢系统的局部放大结构示意图。FIG3 is a partial enlarged structural schematic diagram of the low-carbon hydrocarbon steam reforming hydrogen production system in the present invention.

附图标记:Reference numerals:

1-原料气压缩机;2-原料~饱和蒸汽换热器;3-原料~过热蒸汽换热器;4-脱硫反应器;5-转化炉;6-余热锅炉;7-中温变换反应器;8-除氧水换热器;9-变换气第一分液罐;10-热水换热器;11-除盐水换热器;12-变换气第二分液罐;13-变换气冷却器;14-变换气第三分液罐;15-富氢气体变压吸附系统;16-酸性水汽提塔;17-除氧器;18-除氧水增压泵;19-余锅汽水分离器;20-原料增压泵;21-液相原料~第二分液罐顶气换热器;22-透平~供电系统;23-旁路阀;1-Raw gas compressor; 2-Raw material ~ saturated steam heat exchanger; 3-Raw material ~ superheated steam heat exchanger; 4-Desulfurization reactor; 5-Converter; 6-Waste heat boiler; 7-Medium temperature shift reactor; 8-Deoxygenated water heat exchanger; 9-Conversion gas first liquid separation tank; 10-Hot water heat exchanger; 11-Desalted water heat exchanger; 12-Conversion gas second liquid separation tank; 13-Conversion gas cooler; 14-Conversion gas third liquid separation tank; 15-Hydrogen-rich gas pressure swing adsorption system; 16-Acidic water stripping tower; 17-Deaerator; 18-Deoxygenated water booster pump; 19-Waste boiler steam-water separator; 20-Raw material booster pump; 21-Liquid phase raw material ~ Second liquid separation tank top gas heat exchanger; 22-Turbine ~ Power supply system; 23-Bypass valve;

5-转化炉包括:501-辐射段,502-转化原料预热段、503-蒸汽过热段、504-脱硫原料预热段、505-高温空气预热段、506-饱和水蒸发段、507-低温空气预热段。5-Conversion furnace includes: 501-radiation section, 502-conversion raw material preheating section, 503-steam superheating section, 504-desulfurization raw material preheating section, 505-high temperature air preheating section, 506-saturated water evaporation section, 507-low temperature air preheating section.

具体实施方式DETAILED DESCRIPTION

以下通过具体的实施例对本发明的内容作进一步详细的说明。The present invention is further described in detail below through specific examples.

如无特殊说明,本发明中的转化炉5发生制氢反应的炉管是设置在于转化炉5的辐射段501,辐射段501还包括燃烧室;本发明中的富氢气体变压吸附系统15为市面上常用的变压吸附系统,其至少包括吸附器、缓冲罐、程序控制阀、调节阀及管线等设备;低碳烃水蒸汽重整制氢系统中还能够根据需求设置若干个阀门、流量计、压力计、温度计、泵和其他可用于监测系统的设备(未在图1或2中画出),但相关人员不能以此作为对本发明的实施方式的限定。低碳烃的出料口指的是含碳原子为1~5的烷烃的物料(例如,甲烷、乙烷、丙烷、丁烷、戊烷)的出口,且低碳烃的来源为炼油厂的管路或低碳烃的储料罐;本发明实施例和对比例的低碳烃水蒸汽重整制氢系统中的设备均是通过管路进行连接的。Unless otherwise specified, the furnace tube in which the hydrogen production reaction occurs in the reformer 5 of the present invention is arranged in the radiation section 501 of the reformer 5, and the radiation section 501 also includes a combustion chamber; the hydrogen-rich gas pressure swing adsorption system 15 of the present invention is a commonly used pressure swing adsorption system on the market, which at least includes adsorbers, buffer tanks, program control valves, regulating valves and pipelines and other equipment; the low-carbon hydrocarbon steam reforming hydrogen production system can also be provided with a number of valves, flow meters, pressure gauges, thermometers, pumps and other equipment that can be used for monitoring the system (not shown in Figures 1 or 2) according to demand, but relevant personnel cannot use this as a limitation on the implementation mode of the present invention. The discharge port of low-carbon hydrocarbons refers to the outlet of materials containing alkanes with 1 to 5 carbon atoms (for example, methane, ethane, propane, butane, pentane), and the source of low-carbon hydrocarbons is the pipeline of the refinery or the storage tank of low-carbon hydrocarbons; the equipment in the low-carbon hydrocarbon steam reforming hydrogen production system of the embodiment of the present invention and the comparative example are all connected by pipelines.

除特别说明外,对比例和实施例中使用的变换气冷却器13是型号为GP6*3-6-128-3.0SF-23.4/DR-Ⅲ、厂家为湖北省电力公司汉口电力设备厂的空气冷却器设备;且对比例和实施例中的压力均为表压;对比例和实施例中的“蒸汽碳比”指的是转化炉5设备中的水蒸汽和原料中碳原子摩尔流量之比;本发明中的“低碳烃”指的是甲烷、乙烷、丙烷、丁烷和戊烷的一种或多种。Unless otherwise specified, the conversion gas cooler 13 used in the comparative examples and the embodiments is an air cooler device with a model of GP6*3-6-128-3.0SF-23.4/DR-Ⅲ and a manufacturer of the Hankou Electric Power Equipment Factory of Hubei Electric Power Company; and the pressures in the comparative examples and the embodiments are all gauge pressures; the "steam carbon ratio" in the comparative examples and the embodiments refers to the ratio of the molar flow rate of water vapor in the converter 5 equipment and the carbon atoms in the raw material; the "low carbon hydrocarbons" in the present invention refer to one or more of methane, ethane, propane, butane and pentane.

还需要说明的是,图1和图2中的“去19”、“自8”、“去17”和“自2”分别表示的是“管路与余锅汽水分离器19相连”,“管路与除氧水换热器8相连”、“管路与除氧器17相连”和“管路与富氢气体变压吸附系统15相连”。关于“去19”,还需要说明的是,在本对比例中的余热锅炉系统包括余热锅炉6和余锅汽水分离器19,且两者通过管路连接,原料水(除盐水和回用净化水)实际上是从除氧水换热器8通入余热锅炉系统,并利用转化炉5的饱和水蒸发段506的热量,最终在余锅汽水分离器19形成饱和蒸汽。It should also be noted that "to 19", "from 8", "to 17" and "from 2" in Figures 1 and 2 respectively represent "the pipeline is connected to the waste heat boiler steam-water separator 19", "the pipeline is connected to the deoxygenated water heat exchanger 8", "the pipeline is connected to the deaerator 17" and "the pipeline is connected to the hydrogen-rich gas pressure swing adsorption system 15". Regarding "to 19", it should also be noted that the waste heat boiler system in this comparative example includes the waste heat boiler 6 and the waste heat boiler steam-water separator 19, and the two are connected by a pipeline. The raw water (deionized water and recycled purified water) is actually introduced into the waste heat boiler system from the deoxygenated water heat exchanger 8, and the heat of the saturated water evaporation section 506 of the reformer 5 is used to finally form saturated steam in the waste heat boiler steam-water separator 19.

在实施例中,所述转化气中的氢气含量为65%~73%(体积分数,干基),CO含量为13%~15%(体积分数,干基);In an embodiment, the hydrogen content in the conversion gas is 65% to 73% (volume fraction, dry basis), and the CO content is 13% to 15% (volume fraction, dry basis);

在空气被转化炉的低温空气预热段和高温空气预热段预热至430~450℃后,再在转化炉的燃烧室内发生所述燃烧反应。所述转化炉的空气入口温度为25℃;所述转化炉的炉管入口的温度为580~630℃;所述转化炉的炉管出口的温度为800~900℃、压力为2.84~4.64MPa;所述转化炉的排出烟气的温度为140~152℃,且排出烟气的含氧量≤3%(干基)。After the air is preheated to 430-450°C by the low-temperature air preheating section and the high-temperature air preheating section of the reformer, the combustion reaction occurs in the combustion chamber of the reformer. The air inlet temperature of the reformer is 25°C; the temperature of the furnace tube inlet of the reformer is 580-630°C; the temperature of the furnace tube outlet of the reformer is 800-900°C and the pressure is 2.84-4.64MPa; the temperature of the exhaust flue gas of the reformer is 140-152°C, and the oxygen content of the exhaust flue gas is ≤3% (dry basis).

对比例1Comparative Example 1

低碳烃水蒸汽重整制氢系统:Low-carbon hydrocarbon steam reforming hydrogen production system:

本对比例提供一种低碳烃水蒸汽重整制氢系统(见图1),包括原料气压缩机1;原料~饱和蒸汽换热器2;原料~过热蒸汽换热器3;脱硫反应器4;转化炉5;余热锅炉6;中温变换反应器7;除氧水换热器8;变换气第一分液罐9;热水换热器10;除盐水换热器11;变换气第二分液罐12;变换气冷却器13;变换气第三分液罐14;富氢气体变压吸附系统15;酸性水汽提塔16;除氧器17;除氧水增压泵18和余锅汽水分离器19;The present comparative example provides a low-carbon hydrocarbon steam reforming hydrogen production system (see Figure 1), including a raw gas compressor 1; a raw material-saturated steam heat exchanger 2; a raw material-superheated steam heat exchanger 3; a desulfurization reactor 4; a reformer 5; a waste heat boiler 6; a medium-temperature shift reactor 7; a deoxygenated water heat exchanger 8; a first shift gas separator 9; a hot water heat exchanger 10; a desalted water heat exchanger 11; a second shift gas separator 12; a shift gas cooler 13; a third shift gas separator 14; a hydrogen-rich gas pressure swing adsorption system 15; an acidic water stripping tower 16; a deaerator 17; a deoxygenated water booster pump 18 and a residual boiler steam-water separator 19;

本对比例的低碳烃水蒸汽重整制氢系统结构(见图1和图3),其具体包括:The structure of the low-carbon hydrocarbon steam reforming hydrogen production system of this comparative example (see Figures 1 and 3) specifically includes:

低碳烃的原料气出口,通过管路依次与原料气压缩机1、蒸汽换热器2、原料~过热蒸汽换热器3、脱硫反应器4相连,经过转化炉5的脱硫原料预热段504、转化炉5的转化原料预热段502,再与转化炉5的炉管、余热锅炉6、中温变换反应器7、除氧水换热器8和变换气第一分液罐9相连。The outlet of the raw gas of low-carbon hydrocarbons is connected to the raw gas compressor 1, the steam heat exchanger 2, the raw material-superheated steam heat exchanger 3, and the desulfurization reactor 4 in sequence through pipelines, passes through the desulfurization raw material preheating section 504 of the converter 5, the conversion raw material preheating section 502 of the converter 5, and is then connected to the furnace tube of the converter 5, the waste heat boiler 6, the medium-temperature conversion reactor 7, the deoxygenated water heat exchanger 8 and the first liquid separation tank 9 of the conversion gas.

变换气第一分液罐9的顶部的气体出口,通过管路依次与热水换热器10、除盐水换热器11、变换气第二分液罐12相连;变换气第二分液罐12的顶部的气体出口,通过管路与变换气冷却器13、变换气第三分液罐14和富氢气体变压吸附系统15相连,用于将混合气冷却、分离和纯化得到纯度较高的产品氢和燃料;富氢气体变压吸附系统15设有两个管路出口,一个管路出口,用于输出产品氢出口;一个管路出口与转化炉5的燃烧室相连,用于提供燃料。The gas outlet at the top of the first conversion gas separator 9 is connected to the hot water heat exchanger 10, the desalted water heat exchanger 11, and the second conversion gas separator 12 in sequence through pipelines; the gas outlet at the top of the second conversion gas separator 12 is connected to the conversion gas cooler 13, the third conversion gas separator 14 and the hydrogen-rich gas pressure swing adsorption system 15 through pipelines, and is used to cool, separate and purify the mixed gas to obtain product hydrogen and fuel with higher purity; the hydrogen-rich gas pressure swing adsorption system 15 is provided with two pipeline outlets, one pipeline outlet is used to output the product hydrogen outlet; and the other pipeline outlet is connected to the combustion chamber of the converter 5 for providing fuel.

变换气第三分液罐14的底部,与酸性水汽提塔16的顶部进料口相连;变换气第一分液罐9的底部的液体出口与变换气第二分液罐12的底部的液体出口相连后,再通过管路与酸性水汽提塔16的中间(中部)的进料口相连;酸性水汽提塔16的底部设置有加热蒸汽(1.0MPa蒸汽)的入口和纯净水的出料口管路;用于除去二氧化碳等酸性物质和获得回用纯净水。具体地,酸性水汽提塔16的顶部设置有酸性气体的出口,用于排放微量酸性气体(如,二氧化碳);酸性水汽提塔16的底部的纯净水的出料口管路分为两路,一路与除氧器17的第二进料口相连,用于给除氧器17提供回用纯净水,一路作为污水外排(实质上是水,基本无污染)。The bottom of the third liquid separator 14 of the conversion gas is connected to the top feed port of the acidic water stripping tower 16; the liquid outlet at the bottom of the first liquid separator 9 of the conversion gas is connected to the liquid outlet at the bottom of the second liquid separator 12 of the conversion gas, and then connected to the feed port in the middle (middle) of the acidic water stripping tower 16 through a pipeline; the bottom of the acidic water stripping tower 16 is provided with an inlet for heating steam (1.0MPa steam) and a discharge port pipeline for pure water; it is used to remove acidic substances such as carbon dioxide and obtain recycled pure water. Specifically, the top of the acidic water stripping tower 16 is provided with an outlet for acidic gas, which is used to discharge trace acidic gases (such as carbon dioxide); the discharge port pipeline for pure water at the bottom of the acidic water stripping tower 16 is divided into two routes, one of which is connected to the second feed port of the deaerator 17, which is used to provide recycled pure water to the deaerator 17, and the other is used as sewage discharge (substantially water, basically pollution-free).

除氧器17与蒸汽换热器2的热源出口相连,用于给除氧器17提供加热的热源;同时除氧器17还设置有补充蒸汽的管路,用于补充热源(本对比例不使用)。The deaerator 17 is connected to the heat source outlet of the steam heat exchanger 2 to provide a heat source for heating the deaerator 17; at the same time, the deaerator 17 is also provided with a steam supplementary pipeline for supplementing the heat source (not used in this comparative example).

除盐水换热器11设置有除盐水入口;除盐水换热器11还与除氧器17的第一进料口、除氧水增压泵18、除氧水换热器8、余锅系统(含余热锅炉6和余锅汽水分离器19)相连,用于给余锅汽水分离器19提供饱和水;余锅汽水分离器19的底部设置有经过5的饱和水蒸发段506的管路,用于回收利用转化炉5的热量和产生饱和蒸汽。The desalted water heat exchanger 11 is provided with a desalted water inlet; the desalted water heat exchanger 11 is also connected to the first feed port of the deaerator 17, the deoxygenated water booster pump 18, the deoxygenated water heat exchanger 8, and the waste heat boiler system (including the waste heat boiler 6 and the waste heat boiler steam-water separator 19), so as to provide saturated water to the waste heat boiler steam-water separator 19; a pipeline passing through the saturated water evaporation section 506 of 5 is provided at the bottom of the waste heat boiler steam-water separator 19, so as to recycle the heat of the converter 5 and generate saturated steam.

余锅汽水分离器19还设置有两路饱和蒸汽流出的管路,其中,一路通过管路与原料~饱和蒸汽换热器2和除氧器17相连,用于给原料~饱和蒸汽换热器2和除氧器17提供热源与热量;一路管路与转化炉5的蒸汽过热段503的管路相连,用于回收更高温烟气的热量产生过热蒸汽。之后,蒸汽过热段503的管路同样分为两路,一路直接排空(或外输);一路与原料~过热蒸汽换热器3相连,再与“设置在转化炉5的脱硫原料预热段504和转化炉5的转化原料预热段502之间的管路”相连,用于将过热蒸汽与低碳烃混合、给转化炉5的炉管提供水蒸汽重整制氢的反应气。The residual boiler steam-water separator 19 is also provided with two pipelines for saturated steam to flow out, wherein one pipeline is connected to the raw material-saturated steam heat exchanger 2 and the deaerator 17 through the pipeline, and is used to provide heat source and heat to the raw material-saturated steam heat exchanger 2 and the deaerator 17; one pipeline is connected to the pipeline of the steam superheating section 503 of the reformer 5, and is used to recover the heat of the higher temperature flue gas to generate superheated steam. Afterwards, the pipeline of the steam superheating section 503 is also divided into two routes, one of which is directly emptied (or externally transmitted); one pipeline is connected to the raw material-superheated steam heat exchanger 3, and then connected to the "pipeline set between the desulfurization raw material preheating section 504 of the reformer 5 and the conversion raw material preheating section 502 of the reformer 5", and is used to mix the superheated steam with low-carbon hydrocarbons and provide the furnace tubes of the reformer 5 with water vapor reforming hydrogen production reaction gas.

还需要说明的是,转化炉5(见图3),自高温段(约900℃)到低温段(约150℃)依次包括辐射段501(含燃烧室、补充燃料气入口、热空气入口和解吸气入口),转化原料预热段502、蒸汽过热段503、脱硫原料预热段504、高温空气预热段505、饱和水蒸发段506和低温空气预热段507(含空气入口和排烟口)。It should also be noted that the converter 5 (see Figure 3), from the high temperature section (about 900°C) to the low temperature section (about 150°C), includes in sequence a radiation section 501 (including a combustion chamber, a supplementary fuel gas inlet, a hot air inlet and a desorption gas inlet), a conversion raw material preheating section 502, a steam superheating section 503, a desulfurization raw material preheating section 504, a high temperature air preheating section 505, a saturated water evaporation section 506 and a low temperature air preheating section 507 (including an air inlet and a smoke exhaust port).

上述设备均是通过管路相连。All of the above equipment are connected through pipelines.

低碳烃水蒸汽重整制氢的方法:Method for producing hydrogen by steam reforming of low-carbon hydrocarbons:

本对比例提供一种现有某炼厂的低碳烃水蒸汽重整制氢的方法,以某次运行(产能:2×104Nm3/h)为例,具体包括如下步骤(见图1和图3):This comparative example provides a method for producing hydrogen by steam reforming of low-carbon hydrocarbons in an existing refinery, taking a certain operation (capacity: 2×10 4 Nm 3 /h) as an example, which specifically includes the following steps (see Figures 1 and 3):

原料气(组分:CH4、纯度:甲烷摩尔分数≥97.5%、总硫≤20mg/m3、温度:25℃、压力:0.6MPa、流量:13.1t/h,即18303.3Nm3/h)通过原料气压缩机1增压至3.5MPa(压缩机出口的压力,表压),原料~饱和蒸汽换热器2(热源:饱和蒸汽,244℃)和原料~过热蒸汽换热器3(热源:过热蒸汽,430℃)加热至380℃,脱硫反应器4进行脱硫处理至硫含量低于0.05~0.1ppm,,转化炉5的脱硫原料预热段504预加热至430℃,与中压蒸汽(压力:3.5MPa、温度:365℃、流量:44.1t/h)混合、再一起被转化炉5的转化原料预热段502加热至630℃后,再在转化炉5的炉管进行催化重整制氢反应(反应温度:860℃、反应压力3.0MPa、催化剂Z418、反应耗汽44.1t/h、蒸汽碳比3.0),得到转化气(温度:860℃、压力:2.84MPa、流量:57.2t/h,H2含量72.7%,CO含量13.1%,干基);The raw gas (component: CH 4 , purity: methane molar fraction ≥ 97.5%, total sulfur ≤ 20 mg/m 3 , temperature: 25°C, pressure: 0.6 MPa, flow rate: 13.1 t/h, i.e. 18303.3 Nm 3 /h) is pressurized to 3.5 MPa (pressure at the compressor outlet, gauge pressure) by the raw gas compressor 1, and heated to 380°C by the raw material-saturated steam heat exchanger 2 (heat source: saturated steam, 244°C) and the raw material-superheated steam heat exchanger 3 (heat source: superheated steam, 430°C). The desulfurization reactor 4 performs desulfurization treatment until the sulfur content is less than 0.05-0.1 ppm. The desulfurization raw material preheating section 504 of the reformer 5 is preheated to 430°C and mixed with medium-pressure steam (pressure: 3.5 MPa, temperature: 365°C, flow rate: 44.1t/h) and then heated to 630°C by the reforming raw material preheating section 502 of the reforming furnace 5, and then catalytic reforming hydrogen production reaction is carried out in the furnace tube of the reforming furnace 5 (reaction temperature: 860°C, reaction pressure 3.0MPa, catalyst Z418, reaction steam consumption 44.1t/h, steam carbon ratio 3.0) to obtain reformed gas (temperature: 860°C, pressure: 2.84MPa, flow rate: 57.2t/h, H2 content 72.7%, CO content 13.1%, dry basis);

转化气经余热锅炉6回收热量、直至降温至340℃,进入中温变化反应器7除一氧化碳(温度:410℃、催化剂:B113-2,将一氧化碳和水转化为氢气和二氧化碳)、被除氧水换热器8的冷流体冷却至160℃,在变换气第一分液罐9得到一级变换气(温度:160℃、压力:2.78MPa、流量:51.7t/h)和工艺冷凝水;一级变换气经热水换热器10(冷源:65℃热水,冷源的流量:75t/h)、除盐水换热器11冷却至130℃,在变换气第二分液罐12得到二级变换气(130℃、2.63MPa、流量:41.2t/h)和工艺冷凝水;二级变换气经变换气冷却器13冷却至40℃,在变换气第三分液罐14得到三级变换气(40℃、2.52MPa、流量:34.7t/h)和工艺冷凝水。The reformed gas is heat recovered by the waste heat boiler 6 until the temperature is reduced to 340°C, and then enters the medium temperature change reactor 7 to remove carbon monoxide (temperature: 410°C, catalyst: B113-2, converting carbon monoxide and water into hydrogen and carbon dioxide), and is cooled to 160°C by the cold fluid of the deoxygenated water heat exchanger 8. The first-stage reformed gas (temperature: 160°C, pressure: 2.78MPa, flow rate: 51.7t/h) and process condensed water are obtained in the first liquid separation tank 9 of the reformed gas; the first-stage reformed gas is heated to 400°C and then heated to 800°C. The gas is cooled to 130°C by the heat exchanger 10 (cold source: 65°C hot water, flow rate of the cold source: 75 t/h) and the desalted water heat exchanger 11, and a secondary conversion gas (130°C, 2.63 MPa, flow rate: 41.2 t/h) and process condensed water are obtained in the second conversion gas separator 12; the secondary conversion gas is cooled to 40°C by the conversion gas cooler 13, and a tertiary conversion gas (40°C, 2.52 MPa, flow rate: 34.7 t/h) and process condensed water are obtained in the third conversion gas separator 14.

变换气第一分液罐9和变换气第二分液罐12的工艺冷凝水(温度:160℃、总流量:16.1t/h)、变换气第三分液罐14的工艺冷凝水(温度:40℃、流量:6.5t/h)和1.0MPa蒸汽(温度:185℃、流量:0t/h)分别在酸性水汽提塔16的中部进料、顶部和底部进料,得到酸性气和水(流量:22.5t/h);其中,一步部分水作为污水直接排出,另一部分水作为回用净化水(流量:22.5t/h、温度:112℃)在除氧器17中与加热后的除盐水混合作为原料使用。The process condensate (temperature: 160°C, total flow rate: 16.1 t/h) of the first conversion gas separator 9 and the second conversion gas separator 12, the process condensate (temperature: 40°C, flow rate: 6.5 t/h) of the third conversion gas separator 14 and 1.0 MPa steam (temperature: 185°C, flow rate: 0 t/h) are fed into the middle, top and bottom of the acid water stripping tower 16 respectively to obtain acid gas and water (flow rate: 22.5 t/h); wherein, part of the water is directly discharged as sewage in one step, and the other part of the water is used as recycled purified water (flow rate: 22.5 t/h, temperature: 112°C) and mixed with the heated desalted water in the deaerator 17 for use as raw material.

三级变换气经富氢气体变压吸附系统15变压吸附(PSA)工艺(关键工艺参数:氢气回收率≥90%、吸附剂:多孔固体物质)得到产品氢(流量:4.54t/h、2×104Nm3/h,以体积分数计,氢气的纯度为99.9%)和解吸气(成分:99.9%氢气,流量:30.15t/h、24002Nm3/h,热值:2234.0kcal/Nm3)。The tertiary shifted gas is subjected to a pressure swing adsorption (PSA) process (key process parameters: hydrogen recovery rate ≥ 90%, adsorbent: porous solid material) of the hydrogen-rich gas pressure swing adsorption system 15 to obtain product hydrogen (flow rate: 4.54 t/h, 2×10 4 Nm 3 /h, hydrogen purity is 99.9% by volume fraction) and desorbed gas (composition: 99.9% hydrogen, flow rate: 30.15 t/h, 24002 Nm 3 /h, calorific value: 2234.0 kcal/Nm 3 ).

空气(流量:102t/h、温度:25℃)被转化炉5的低温空气预热段507、高温空气预热段505加热至430℃的热空气,解吸气(流量:30.15t/h)和补充燃料气(组分:CH4、流量:1.53t/h)三种气体在转化炉5的燃烧室混合、燃烧产生高温烟气(约900℃),给转化炉5提供热量;且转化炉5的排烟温度(即排出的烟气的温度)为150.4℃,干基含氧量为3%(体积分数)。The air (flow rate: 102 t/h, temperature: 25°C) is heated to 430°C by the low-temperature air preheating section 507 and the high-temperature air preheating section 505 of the reformer 5. The three gases, the desorbed gas (flow rate: 30.15 t/h) and the supplementary fuel gas (component: CH 4 , flow rate: 1.53 t/h), are mixed and burned in the combustion chamber of the reformer 5 to generate high-temperature flue gas (about 900°C) to provide heat for the reformer 5; and the exhaust gas temperature of the reformer 5 (i.e. the temperature of the exhaust flue gas) is 150.4°C, and the dry basis oxygen content is 3% (volume fraction).

除盐水(流量:42.84t/h、温度:30℃)经除盐水换热器11加热至110℃,和16塔底产的回用净化水(流量:22.5,温度:112℃)混合后,再在除氧器17除氧、18除氧水增压泵增压至5.2MPa、除氧水换热器8加热至265℃、进一步加热余热锅炉6至267℃后,并利用转化炉5的饱和水蒸发段506的热量,在余锅汽水分离器19得到3.5MPa饱和蒸汽(流量:67.5t/h、温度244℃)。余热锅炉6与余锅汽水分离器19构成的余热锅炉系统的产汽压力为3.5MPa。Desalted water (flow rate: 42.84 t/h, temperature: 30°C) is heated to 110°C by desalted water heat exchanger 11, mixed with recycled purified water (flow rate: 22.5, temperature: 112°C) produced at the bottom of tower 16, deoxygenated by deaerator 17, pressurized to 5.2MPa by deoxygenated water booster pump 18, heated to 265°C by deoxygenated water heat exchanger 8, further heated to 267°C by waste heat boiler 6, and using the heat of saturated water evaporation section 506 of reformer 5, 3.5MPa saturated steam (flow rate: 67.5t/h, temperature 244°C) is obtained in waste heat boiler steam-water separator 19. The steam production pressure of the waste heat boiler system composed of waste heat boiler 6 and waste heat boiler steam-water separator 19 is 3.5MPa.

饱和蒸汽经转化炉5的蒸汽过热段503的烟气加热后得到过热蒸汽(流量:65.3t/h,温度:430℃);剩余的饱和蒸汽(流量:2.2t/h)作为热源给原料~饱和蒸汽换热器2提供热量,这一部分的饱和蒸汽(244℃)作为原料~饱和蒸汽换热器2的热源后,再作为除氧器17的热源(220℃)进行热量的回收利用,能够将除氧器17中的原料加热至118℃。The saturated steam is heated by the flue gas of the steam superheating section 503 of the converter 5 to obtain superheated steam (flow rate: 65.3 t/h, temperature: 430°C); the remaining saturated steam (flow rate: 2.2 t/h) is used as a heat source to provide heat to the raw material-saturated steam heat exchanger 2. This part of the saturated steam (244°C) is used as a heat source for the raw material-saturated steam heat exchanger 2, and then used as a heat source (220°C) for the deaerator 17 to recover heat, which can heat the raw material in the deaerator 17 to 118°C.

过热蒸汽分为两部分,一部分(流量:21.2t/h)外输;一部分(流量:44.1t/h)用于冷却原料~过热蒸汽换热器3,得到中压蒸汽,该中压蒸汽是用于进行催化重整制氢反应。The superheated steam is divided into two parts, one part (flow rate: 21.2t/h) is exported; the other part (flow rate: 44.1t/h) is used to cool the raw material-superheated steam heat exchanger 3 to obtain medium-pressure steam, which is used for catalytic reforming hydrogen production reaction.

系统和工艺的补充说明:Additional explanation of system and process:

酸性水汽提塔16实际是20m高的填料塔;酸性水汽提塔16的1.0MPa蒸汽的流量为0.1t/h;酸性水汽提塔16是除去微量CO2等杂质,最终二氧化碳是以酸性气体形成在酸性水汽提塔16塔顶排出的。The acidic water stripping tower 16 is actually a 20m high packed tower; the flow rate of 1.0MPa steam in the acidic water stripping tower 16 is 0.1t/h; the acidic water stripping tower 16 removes trace impurities such as CO2 , and finally the carbon dioxide is discharged from the top of the acidic water stripping tower 16 in the form of acidic gas.

解吸气作为主要燃料为转化炉提供热量,天然气做辅助燃料,与预热后的高温空气混合后送入转化炉燃烧室燃烧,高温烟气在辐射段501为蒸汽重整反应提供热量,随后依次通过转化原料预热段502、蒸汽过热段503、脱硫原料预热段504、高温空气预热段505、饱和水蒸发段506、低温空气预热段降温507,控制转化炉出口烟气氧含量为3%(干基)。The desorbed gas is used as the main fuel to provide heat for the converter, and natural gas is used as the auxiliary fuel. After being mixed with the preheated high-temperature air, it is sent into the combustion chamber of the converter for combustion. The high-temperature flue gas provides heat for the steam reforming reaction in the radiation section 501, and then passes through the conversion raw material preheating section 502, the steam superheating section 503, the desulfurization raw material preheating section 504, the high-temperature air preheating section 505, the saturated water evaporation section 506, and the low-temperature air preheating section cooling 507 in sequence to control the oxygen content of the flue gas at the outlet of the converter to be 3% (dry basis).

变压吸附(PSA)工艺具体为:吸附、顺向降压、逆向放压、冲洗、升压。The specific process of pressure swing adsorption (PSA) is as follows: adsorption, forward pressure reduction, reverse pressure release, flushing, and pressure increase.

实施例1Example 1

与对比例1相比,本实施例的低耗能的低碳烃水蒸汽重整制氢系统还包括液相原料~第二分液罐顶气换热器21、透平~供电系统22和旁路阀23,并改动了变换气冷却器13的接入方式。Compared with Comparative Example 1, the low-energy low-carbon hydrocarbon steam reforming hydrogen production system of this embodiment also includes a liquid-phase raw material-second liquid separation tank top gas heat exchanger 21, a turbine-power supply system 22 and a bypass valve 23, and the access method of the conversion gas cooler 13 is changed.

低耗能的低碳烃水蒸汽重整制氢系统:Low-energy-consuming low-carbon hydrocarbon steam reforming hydrogen production system:

本实施例的低耗能的低碳烃水蒸汽重整制氢系统的结构示意图,具体如图2和图3所示;且本实施例的低耗能的低碳烃水蒸汽重整制氢系统的结构是基于对比例的基础上改动得到的;其改动具体如下:The structural schematic diagram of the low-energy-consuming low-carbon hydrocarbon steam reforming hydrogen production system of this embodiment is specifically shown in Figures 2 and 3; and the structure of the low-energy-consuming low-carbon hydrocarbon steam reforming hydrogen production system of this embodiment is modified based on the comparative example; the specific modifications are as follows:

1)停用原料气压缩机1,并在相应的位置增设原料增压泵20用于液态的低碳烃进料、增压和加热;1) Stop the raw gas compressor 1, and add a raw material booster pump 20 at the corresponding position for feeding, pressurizing and heating liquid low-carbon hydrocarbons;

2)在原料增压泵20和原料~饱和蒸汽换热器2之间的管路上,增设液相原料~第二分液罐顶气换热器21;2) A liquid phase raw material-second liquid separation tank top gas heat exchanger 21 is added to the pipeline between the raw material booster pump 20 and the raw material-saturated steam heat exchanger 2;

3)变换气第二分液罐12的顶部的气体出口的管路改为:依次与液相原料~第二分液罐顶气换热器21、变换气冷却器13和变换气第三分液罐14相连,用于回收变换气第二分液罐12的热量给液相原料~第二分液罐顶气换热器21加热,并降低变换气冷却器13的耗能(见表1),从而获得三级变换气和工艺冷凝水;3) The pipeline of the gas outlet at the top of the second liquid separator 12 of the conversion gas is changed to: connected to the liquid-phase raw material-second liquid separator top gas heat exchanger 21, the conversion gas cooler 13 and the third liquid separator 14 of the conversion gas in sequence, so as to recover the heat of the second liquid separator 12 of the conversion gas to heat the liquid-phase raw material-second liquid separator top gas heat exchanger 21 and reduce the energy consumption of the conversion gas cooler 13 (see Table 1), thereby obtaining the three-stage conversion gas and process condensed water;

4)在转化炉5的转化气出口和余热锅炉6之间增设透平~供电系统22和旁路阀23;透平~供电系统22和旁路阀23是以并联方式接入的,用于方便条件透平~供电系统22的压力,并回收部分转化气中的内能。4) A turbine-power supply system 22 and a bypass valve 23 are added between the reformed gas outlet of the reformer 5 and the waste heat boiler 6; the turbine-power supply system 22 and the bypass valve 23 are connected in parallel to facilitate the pressure of the turbine-power supply system 22 and to recover part of the internal energy in the reformed gas.

本实施例中使用的原料增压泵20为离心泵。The raw material booster pump 20 used in this embodiment is a centrifugal pump.

本实施例中使用的透平~供电系统22包括透平膨胀机和发电设备。透平膨胀机和发电设备是通过可传动的链接件进行连接的。透平膨胀机是能够将内能转化为机械能的设备,发电设备是能够将机械能转化为电能的设备。此外,发电设备还能够与储能设备或输出电能的导线连接,用于储能、将电能直接输出或直接用于本实施例系统中的设备,进一步降低能耗。The turbine-power supply system 22 used in this embodiment includes a turbine expander and a power generation device. The turbine expander and the power generation device are connected through a drivable link. The turbine expander is a device that can convert internal energy into mechanical energy, and the power generation device is a device that can convert mechanical energy into electrical energy. In addition, the power generation device can also be connected to an energy storage device or a wire that outputs electrical energy, for energy storage, direct output of electrical energy, or direct use of electrical energy in the device in the system of this embodiment, further reducing energy consumption.

还需要说明的是,本实施例的低碳烃水蒸汽重整制氢系统是通过停用原料气压缩机1及其相关的管路、增设管路和阀门的手段来保留原有管路和设备功能;且原料气压缩机1与原料增压泵20以并联方式的接入系统的,两者之间还可以通过管路增设气液分离器,为气液混合进料进一步创设条件。如果原料包括气体和液态的低碳烃时,可通过打开相关设备(如原料气压缩机1)和相应阀门实现气态和液态的低碳烃混合进料,调整相关管路的流量,同样实现降低耗能的低碳烃催化重整制氢的工艺。It should also be noted that the low-carbon hydrocarbon steam reforming hydrogen production system of this embodiment retains the original pipeline and equipment functions by means of deactivating the raw gas compressor 1 and its related pipelines, adding pipelines and valves; and the raw gas compressor 1 and the raw material booster pump 20 are connected to the system in parallel, and a gas-liquid separator can be added between the two through the pipeline to further create conditions for gas-liquid mixed feeding. If the raw materials include gaseous and liquid low-carbon hydrocarbons, the mixed feeding of gaseous and liquid low-carbon hydrocarbons can be achieved by opening the relevant equipment (such as the raw gas compressor 1) and the corresponding valves, adjusting the flow of the relevant pipelines, and also realizing the process of low-carbon hydrocarbon catalytic reforming hydrogen production with reduced energy consumption.

低耗能的低碳烃水蒸汽重整制氢的方法:Low-energy method for producing hydrogen by steam reforming of low-carbon hydrocarbons:

本实施例提供一种改进后的低耗能的低碳烃水蒸汽重整制氢的工艺,以某次运行(产能:2×104Nm3/h)为例,具体如下(工艺流程参见图2):This embodiment provides an improved low-energy-consuming low-carbon hydrocarbon steam reforming hydrogen production process, taking a certain operation (capacity: 2×10 4 Nm 3 /h) as an example, the details are as follows (see Figure 2 for the process flow):

原料(组分:液态的C3H6、纯度:丙烷摩尔分数≥95%、总硫≤10mg/m3、温度:35℃、压力:1.5MPa、流量:14.7t/h,即7466Nm3/h)通过原料增压泵20增压至4.0MPa(压缩机出口的压力,表压),液相原料~第二分液罐顶气换热器21(热源:二级变换气,130℃)、原料~饱和蒸汽换热器2(热源:饱和蒸汽,252℃)和原料~过热蒸汽换热器3(热源:过热蒸汽,430℃)加热至380℃,脱硫反应器4进行脱硫处理,转化炉5的脱硫原料预热段504预加热至430℃,与中压蒸汽(压力:4.0MPa、温度:375℃、流量:54t/h)混合、再一起被转化炉5的转化原料预热段502加热至630℃后,再在转化炉5的炉管进行催化重整制氢反应(温度:860℃、反应压力:3.5MPa、催化剂:Z418、反应耗汽:54t/h、蒸汽碳比3.0),得到转化气(温度:860℃、压力:3.34Mpa、流量:68.7t/h,H2含量68.1%,CO含量14.7%,干基);The raw material (component: liquid C 3 H 6 , purity: propane mole fraction ≥ 95%, total sulfur ≤ 10 mg/m 3 , temperature: 35°C, pressure: 1.5 MPa, flow rate: 14.7 t/h, i.e. 7466 Nm 3 /h) is pressurized to 4.0 MPa (pressure at the compressor outlet, gauge pressure) by the raw material booster pump 20, and heated to 380°C by the liquid raw material-second liquid separation tank top gas heat exchanger 21 (heat source: secondary conversion gas, 130°C), raw material-saturated steam heat exchanger 2 (heat source: saturated steam, 252°C) and raw material-superheated steam heat exchanger 3 (heat source: superheated steam, 430°C), the desulfurization reactor 4 performs desulfurization treatment, the desulfurization raw material preheating section 504 of the converter 5 is preheated to 430°C, and mixed with the medium pressure Steam (pressure: 4.0MPa, temperature: 375°C, flow rate: 54t/h) is mixed, and then heated to 630°C by the reforming raw material preheating section 502 of the reforming furnace 5, and then a catalytic reforming hydrogen production reaction (temperature: 860°C, reaction pressure: 3.5MPa, catalyst: Z418, reaction steam consumption: 54t/h, steam carbon ratio 3.0) is carried out in the furnace tube of the reforming furnace 5 to obtain reformed gas (temperature: 860°C, pressure: 3.34Mpa, flow rate: 68.7t/h, H2 content 68.1%, CO content 14.7%, dry basis);

转化气先通过并联的透平~供电系统22和旁路阀23回收和循环利用内能(回收的能源/对外做功:1510.45kW,等熵效率η=75%),透平~供电系统22的出口气体(832℃、2.84MPa),再利用余热锅炉6回收热量、直至降温至340℃,进入中温变化反应器7进行除一氧化碳、被除氧水换热器8的冷流体冷却至160℃,在变换气第一分液罐9得到一级变换气(温度:160℃、压力:2.78MPa、流量:60.2t/h)和工艺冷凝水;一级变换气经热水换热器10(冷源:65℃热水,冷源的流量:77.2t/h)、除盐水换热器11冷却至130℃,在变换气第二分液罐12得到二级变换气(130℃、2.63MPa、流量:49.1t/h)和工艺冷凝水;The reformed gas first passes through the parallel turbine-power supply system 22 and the bypass valve 23 to recover and recycle the internal energy (recovered energy/external work: 1510.45kW, isentropic efficiency η=75%), and the outlet gas (832°C, 2.84MPa) of the turbine-power supply system 22 is then heat recovered by the waste heat boiler 6 until the temperature is reduced to 340°C, and then enters the medium temperature change reactor 7 to remove carbon monoxide, and is cooled to 160°C by the cold fluid of the deoxygenated water heat exchanger 8. The first shift gas separator 9 obtains the first shift gas (temperature: 160°C, pressure: 2.78MPa, flow rate: 60.2t/h) and process condensed water; the first shift gas is cooled to 130°C by the hot water heat exchanger 10 (cold source: 65°C hot water, flow rate of cold source: 77.2t/h) and the desalted water heat exchanger 11, and the second shift gas (130°C, 2.63MPa, flow rate: 49.1t/h) and process condensed water are obtained in the second shift gas separator 12;

二级变换气经变换气经21预冷却至115℃,再通过冷却器13冷却至40℃,在变换气第三分液罐14得到三级变换气(40℃、2.52MPa、流量:42.2t/h)和工艺冷凝水。The secondary conversion gas is pre-cooled to 115°C by conversion gas 21, and then cooled to 40°C by cooler 13, and the tertiary conversion gas (40°C, 2.52MPa, flow rate: 42.2t/h) and process condensed water are obtained in the third conversion gas separator 14.

变换气第一分液罐9和变换气第二分液罐12的工艺冷凝水(温度:133℃、总流量:19.7t/h)、变换气第三分液罐14的工艺冷凝水(温度:40℃、流量:6.9t/h)和1.0MPa蒸汽(温度:184℃、流量:0.1t/h)分别在酸性水汽提塔16的中部进料、顶部和底部进料,得到酸性气和水(流量:26.5t/h);其中,一步部分水作为污水直接排出,另一部分水作为回用净化水(流量:26.5t/h、温度:115℃)在除氧器17中与加热后的除盐水混合作为原料使用。The process condensate (temperature: 133°C, total flow rate: 19.7 t/h) of the first conversion gas separator 9 and the second conversion gas separator 12, the process condensate (temperature: 40°C, flow rate: 6.9 t/h) of the third conversion gas separator 14 and 1.0 MPa steam (temperature: 184°C, flow rate: 0.1 t/h) are respectively fed into the middle, top and bottom of the acid water stripping tower 16 to obtain acid gas and water (flow rate: 26.5 t/h); wherein, part of the water is directly discharged as sewage in one step, and the other part of the water is used as recycled purified water (flow rate: 26.5 t/h, temperature: 115°C) and mixed with the heated desalted water in the deaerator 17 for use as raw material.

三级变换气经富氢气体变压吸附系统15变压吸附(PSA)工艺得到产品氢(流量:4.54t/h、2×104Nm3/h,以体积分数计,氢气的纯度为99.9%)和解吸气(成分:99.9%氢气,流量:37.63t/h、28112.2Nm3/h,热值:2034.3kcal/Nm3)。The tertiary shifted gas is subjected to a pressure swing adsorption (PSA) process of a hydrogen-rich gas pressure swing adsorption system 15 to obtain product hydrogen (flow rate: 4.54 t/h, 2×10 4 Nm 3 /h, hydrogen purity is 99.9% by volume fraction) and desorbed gas (composition: 99.9% hydrogen, flow rate: 37.63 t/h, 28112.2 Nm 3 /h, calorific value: 2034.3 kcal/Nm 3 ).

空气(流量:98t/h、温度:25℃)被转化炉5的低温空气预热段507、高温空气预热段505加热至430℃的热空气,解吸气(流量:37.63t/h)和补充燃料气(组分:CH4、流量:0.83t/h)三种气体在转化炉5的燃烧室混合、燃烧产生高温烟气(约900℃),给转化炉5提供热量;且转化炉5的排烟温度(即排出的烟气的温度)为150.4℃,干基含氧量为3%(体积分数)。The air (flow rate: 98 t/h, temperature: 25°C) is heated to 430°C by the low-temperature air preheating section 507 and the high-temperature air preheating section 505 of the reformer 5. The three gases, the desorbed gas (flow rate: 37.63 t/h) and the supplementary fuel gas (component: CH 4 , flow rate: 0.83 t/h), are mixed and burned in the combustion chamber of the reformer 5 to generate high-temperature flue gas (about 900°C) to provide heat for the reformer 5; and the exhaust gas temperature of the reformer 5 (i.e. the temperature of the exhaust flue gas) is 150.4°C, and the dry basis oxygen content is 3% (volume fraction).

除盐水(流量:41.4t/h、温度:30℃)经除盐水换热器11加热至125℃,和16塔底产的回用净化水(流量:26.5t/h,温度:115℃)混合后,再在除氧器17除氧、18除氧水增压泵增压至5.2MPa、除氧水换热器8加热至265℃、进一步加热余热锅炉6至267℃后,并利用转化炉5的饱和水蒸发段506的热量,在余锅汽水分离器19得到4.0MPa饱和蒸汽(流量:70.9t/h、温度252℃)。余热锅炉6与余锅汽水分离器19构成的余热锅炉系统的产汽压力为4.0MPa。Desalted water (flow rate: 41.4 t/h, temperature: 30°C) is heated to 125°C by desalted water heat exchanger 11, mixed with recycled purified water (flow rate: 26.5 t/h, temperature: 115°C) produced at the bottom of tower 16, deoxygenated by deaerator 17, pressurized to 5.2 MPa by deoxygenated water booster pump 18, heated to 265°C by deoxygenated water heat exchanger 8, further heated to 267°C by waste heat boiler 6, and using the heat of saturated water evaporation section 506 of reformer 5, 4.0 MPa saturated steam (flow rate: 70.9 t/h, temperature 252°C) is obtained in waste heat boiler steam-water separator 19. The steam production pressure of the waste heat boiler system composed of waste heat boiler 6 and waste heat boiler steam-water separator 19 is 4.0 MPa.

4.0MPa饱和蒸汽经转化炉5的蒸汽过热段503的烟气加热后得到过热蒸汽(流量:68t/h,温度:430℃);剩余的4.0MPa饱和蒸汽(流量:2.9t/h)作为热源给原料~饱和蒸汽换热器2提供热量,这一部分的4.0MPa饱和蒸汽(252℃)作为原料~饱和蒸汽换热器2的热源后,再作为除氧器17的热源(248℃)进行热量的回收利用,能够将除氧器17中的原料加热至126℃。4.0MPa saturated steam is heated by the flue gas of the steam superheating section 503 of the converter 5 to obtain superheated steam (flow rate: 68t/h, temperature: 430℃); the remaining 4.0MPa saturated steam (flow rate: 2.9t/h) is used as a heat source to provide heat to the raw material-saturated steam heat exchanger 2. This part of 4.0MPa saturated steam (252℃) is used as the heat source of the raw material-saturated steam heat exchanger 2, and then used as the heat source (248℃) of the deaerator 17 for heat recovery and utilization, so that the raw material in the deaerator 17 can be heated to 126℃.

过热蒸汽分为两部分,一部分(流量:14t/h)直接排出;一部分(流量:54t/h)用于原料~过热蒸汽换热器3,得到中压蒸汽,该中压蒸汽是用于进行催化重整制氢反应。The superheated steam is divided into two parts, one part (flow rate: 14t/h) is directly discharged; the other part (flow rate: 54t/h) is used for the raw material-superheated steam heat exchanger 3 to obtain medium-pressure steam, which is used for catalytic reforming hydrogen production reaction.

实施例是基于对比例基础上的改进,其他未具体描述的设备和参数基本与对比例相同。在实施例和对比例中的系统的设备、装置或系统连接方式如无特殊说明,基本均为管路连接,属于本领域的常规技术。同时,为了方便系统的运行,该系统的管路上还设有流量计、温度计和压力计等设备,也属于本领域的常规技术。The embodiments are improvements based on the comparative examples, and other equipment and parameters not specifically described are basically the same as those of the comparative examples. Unless otherwise specified, the equipment, devices or system connection methods of the systems in the embodiments and comparative examples are basically pipeline connections, which belong to the conventional technology in the art. At the same time, in order to facilitate the operation of the system, the pipeline of the system is also provided with equipment such as flow meters, thermometers and pressure gauges, which also belong to the conventional technology in the art.

能耗对比Energy consumption comparison

由于对比例1和实施例1的原料中的低碳烃的来源可以是炼油厂的某个管路或产品,对比例1与实施例1的主要能耗,如表1所示。Since the source of the low-carbon hydrocarbons in the raw materials of Comparative Example 1 and Example 1 can be a pipeline or product of an oil refinery, the main energy consumption of Comparative Example 1 and Example 1 is shown in Table 1.

表1对比例1和实施例1主要能耗Table 1 Main energy consumption of comparative example 1 and embodiment 1

注:表1中的变化量为实施例1的量减去对比例1的量得出的;表1中的冷却水负荷是计算了变换气冷却器13和原料气压缩机1级间冷却的冷却负荷之和得出;表1中的产汽是根据余热锅炉系统产饱和蒸汽总量减去原料~过热蒸汽换热器3和去原料~饱和蒸汽换热器2的蒸汽量计算得出。除变化量外,表1中的正数表示的对系统做功或提供能源的影响因素,而负数表示系统对外做功或损失能源的影响因素。Note: The change in Table 1 is obtained by subtracting the amount of comparative example 1 from the amount of example 1; the cooling water load in Table 1 is calculated by calculating the sum of the cooling loads of the conversion gas cooler 13 and the interstage cooling of the raw gas compressor 1; the steam production in Table 1 is calculated based on the total saturated steam produced by the waste heat boiler system minus the steam amount of the raw material-superheated steam heat exchanger 3 and the steam amount of the raw material-saturated steam heat exchanger 2. In addition to the change, the positive numbers in Table 1 represent the factors affecting the system's work or energy supply, while the negative numbers represent the factors affecting the system's external work or energy loss.

结合表1可知,在氢气产量和纯度相同的前提下,相较于对比例1,实施例1的能耗情况如下:It can be seen from Table 1 that, under the premise of the same hydrogen output and purity, compared with Comparative Example 1, the energy consumption of Example 1 is as follows:

1.经计算,原料增压耗功由对比例1的1349.41kW降至实施例1的28.57kW,减少1320.84kw;1. After calculation, the power consumption of raw material pressurization is reduced from 1349.41kW in comparative example 1 to 28.57kW in embodiment 1, a reduction of 1320.84kw;

2.透平做功1510.45kW(等熵效率η=75%),用于外输电网或驱动装置内其他耗电设备;2. The turbine produces 1510.45 kW of work (isentropic efficiency η = 75%), which is used for external transmission to the power grid or other power-consuming equipment in the drive device;

3.制氢原料增加1.6t/h,但解吸气增产,使转化炉补燃减少0.7t/h;3. The hydrogen production raw materials increased by 1.6t/h, but the desorption gas production increased, which reduced the reformer supplementary combustion by 0.7t/h;

4.中压产汽量降低7.27t/h。4. Medium pressure steam production decreased by 7.27t/h.

5.基于GB/T50441-2016《石油化工设计能耗计算标准》取能耗指标:5. Based on GB/T50441-2016 "Petrochemical Design Energy Consumption Calculation Standard" energy consumption indicators:

5.0MPa蒸汽90kgEO/t、3.5MPa蒸汽88kgEO/t、电0.22kgEO/kwh、除盐水1.0kgEO/t,并原料和燃料按低发热量折成标油(甲烷1195.2kgEO/t、丙烷1107kgEO/t)以及产氢量4.54t/h计算,实施例1的综合能耗减少135.8kgEo/t H25.0MPa steam 90kgEO/t, 3.5MPa steam 88kgEO/t, electricity 0.22kgEO/kwh, demineralized water 1.0kgEO/t, raw materials and fuels converted into standard oil (methane 1195.2kgEO/t, propane 1107kgEO/t) based on low calorific value and hydrogen production 4.54t/h, the comprehensive energy consumption of Example 1 is reduced by 135.8kgEo/t H 2 .

实施例2Example 2

本实施例使用的低耗能的低碳烃水蒸汽重整制氢系统,与实施例1相同。The low-energy-consuming low-carbon hydrocarbon steam reforming hydrogen production system used in this embodiment is the same as that in Example 1.

本实施例提供一种低耗能的低碳烃水蒸汽重整制氢的工艺,同样以某次运行(产能:2×104Nm3/h)为例,与实施例1相比,其关键的工艺参数如下:This embodiment provides a low-energy-consuming process for producing hydrogen by steam reforming of low-carbon hydrocarbons. Taking a certain operation (capacity: 2×10 4 Nm 3 /h) as an example, compared with Embodiment 1, its key process parameters are as follows:

1)原料丙烷(16.1t/h、35℃、1.5MPa、液态)经原料增压泵20增压至5.3MPa,耗功47.46kW。1) Raw material propane (16.1 t/h, 35° C., 1.5 MPa, liquid) is pressurized to 5.3 MPa by raw material booster pump 20, consuming 47.46 kW of power.

2)控制催化重整制氢反应的反应压力4.8MPa,转化炉5中的炉管的蒸汽碳比3.0,转化炉出口的转化气(温度:860℃、压力:4.64Mpa,H2含量66.1%,CO含量13.8%,干基)。2) Control the reaction pressure of the catalytic reforming hydrogen production reaction to 4.8 MPa, the steam-to-carbon ratio of the furnace tube in the reformer 5 to 3.0, and the reformed gas at the reformer outlet (temperature: 860°C, pressure: 4.64 MPa, H2 content 66.1%, CO content 13.8%, dry basis).

3)膨胀透平回收的能源为4744.1kW,透平~供电系统22的出口气体778.6℃、2.84MPa,在余热锅炉系统的19余锅汽水分离产5.0MPa饱和蒸汽(81.6t/h),其中,4.0t/h用于加热原料,77.6t/h用于被转化炉5的蒸汽过热段503的烟气加热至430℃,得到过热蒸汽。3) The energy recovered by the expansion turbine is 4744.1kW, the outlet gas of the turbine-power supply system 22 is 778.6℃ and 2.84MPa, and 5.0MPa saturated steam (81.6t/h) is produced by steam-water separation in the waste heat boiler system 19, of which 4.0t/h is used to heat the raw materials, and 77.6t/h is used to heat the flue gas of the steam superheating section 503 of the converter 5 to 430℃ to obtain superheated steam.

4)过热蒸汽分为两部分,一部分(流量:18.6t/h)直接外输;一部分(流量:59t/h)用于冷却原料~过热蒸汽换热器3,得到中压蒸汽,该中压蒸汽是用于进行催化重整制氢反应;最终制得产品氢(H2纯度:99.9%、流量:2×104Nm3/h即4.54t/h)和解吸气(用于做转化炉燃料,流量:30211.9Nm3/h即39.71t/h,热值:2374.12kcal/Nm3)。4) The superheated steam is divided into two parts, one part (flow rate: 18.6 t/h) is directly output; the other part (flow rate: 59 t/h) is used to cool the raw material-superheated steam heat exchanger 3 to obtain medium-pressure steam, which is used for catalytic reforming hydrogen production reaction; finally, product hydrogen ( H2 purity: 99.9%, flow rate: 2× 104 Nm3 /h, i.e. 4.54 t/h) and desorption gas (used as reformer fuel, flow rate: 30211.9 Nm3 /h, i.e. 39.71 t/h, calorific value: 2374.12 kcal/ Nm3 ) are obtained.

5)辅助燃料(成分:CH4,0.23t/h)。转化炉排烟150.4℃,干基含氧量3%v。转化炉的原料空气(流量:110t/h、温度:25℃)。5) Auxiliary fuel (composition: CH 4 , 0.23 t/h). Exhaust gas of the reformer at 150.4°C, oxygen content on a dry basis at 3%v. Raw air of the reformer (flow rate: 110 t/h, temperature: 25°C).

6)需调整除盐水和回用净化水的用量,本案例中除盐水流量46.6t/h,回用净化水30.8t/h;其余工艺条件基本参照实施例1。6) The amount of desalted water and recycled purified water needs to be adjusted. In this case, the flow rate of desalted water is 46.6 t/h and the recycled purified water is 30.8 t/h. The other process conditions are basically the same as those in Example 1.

能耗对比Energy consumption comparison

由于对比例1和实施例2的原料中的低碳烃的来源可以是炼油厂的某个管路或产品,采用与表1同样的计算方法和计算依据,对比例1与实施例2的主要能耗如表2所示。Since the source of the low-carbon hydrocarbons in the raw materials of Comparative Example 1 and Example 2 can be a pipeline or product of an oil refinery, the same calculation method and basis as in Table 1 are used. The main energy consumption of Comparative Example 1 and Example 2 is shown in Table 2.

表2对比例1和实施例2的主要能耗参数Table 2 Main energy consumption parameters of comparative example 1 and embodiment 2

注:表2中的变化量为实施例2的量减去对比例1的量得出的;表2中的冷却水负荷是计算了变换气冷却器13和原料气压缩机1级间冷却的冷却负荷之和得出;表2中的产汽是根据余热锅炉系统产饱和蒸汽总量减去原料~过热蒸汽换热器3和去原料~饱和蒸汽换热器2的蒸汽量计算得出。除变化量外,表2中的正数表示的对系统做功或提供能源的影响因素,而负数表示系统对外做功或损失能源的影响因素。Note: The change in Table 2 is obtained by subtracting the amount of Example 2 from the amount of Comparative Example 1; the cooling water load in Table 2 is calculated by calculating the sum of the cooling loads of the conversion gas cooler 13 and the interstage cooling of the raw gas compressor 1; the steam production in Table 2 is calculated based on the total saturated steam produced by the waste heat boiler system minus the steam amount of the raw material-superheated steam heat exchanger 3 and the steam amount of the raw material-saturated steam heat exchanger 2. In addition to the change, the positive numbers in Table 2 represent the factors affecting the system's work or energy supply, while the negative numbers represent the factors affecting the system's external work or energy loss.

结合表2可知,在氢气产量和纯度相同的前提下,相较于对比例1,实施例2的能耗情况如下:It can be seen from Table 2 that, under the premise of the same hydrogen output and purity, compared with Comparative Example 1, the energy consumption of Example 2 is as follows:

1、经计算,原料增压耗功由对比例1的1349.41kW降至实施例1的47.46kW,减少1301.95kw;1. After calculation, the power consumption of raw material pressurization is reduced from 1349.41kW in comparative example 1 to 47.46kW in embodiment 1, a reduction of 1301.95kw;

2、膨胀透平做功4744.11kW(等熵效率η=75%),用于外输电网或驱动装置内其他耗电设备;2. The expansion turbine produces 4744.11 kW of work (isentropic efficiency η = 75%), which is used for external transmission to the power grid or other power-consuming equipment in the drive device;

3、制氢原料增加2.95t/h,但解吸气增产,使转化炉补燃减少1.29t/h;3. The hydrogen production raw materials increased by 2.95t/h, but the desorption gas production increased, which reduced the reformer supplementary combustion by 1.29t/h;

4、中压产汽量降低2.58t/h。4. Medium pressure steam production is reduced by 2.58t/h.

5、基于GB/T50441-2016《石油化工设计能耗计算标准》取能耗指标:5.0MPa蒸汽90kgEO/t、3.5MPa蒸汽88kgEO/t、电0.22kgEO/kwh、除盐水1.0kgEO/t,并原料和燃料按低发热量折成标油(甲烷1195.2kgEO/t、丙烷1107kgEO/t)以及产氢量4.54t/h计算,装置综合能耗减少212.53kgEo/t H25. Based on GB/T50441-2016 "Petrochemical Design Energy Consumption Calculation Standard", the energy consumption indicators are: 5.0MPa steam 90kgEO/t, 3.5MPa steam 88kgEO/t, electricity 0.22kgEO/kwh, demineralized water 1.0kgEO/t, and raw materials and fuels are converted into standard oil (methane 1195.2kgEO/t, propane 1107kgEO/t) according to low calorific value, and the hydrogen production is 4.54t/h. The comprehensive energy consumption of the device is reduced by 212.53kgEo/t H2 .

实施例3Example 3

本实施例使用的低耗能的低碳烃水蒸汽重整制氢系统,与实施例2或实施例1相同。The low-energy low-carbon hydrocarbon steam reforming hydrogen production system used in this embodiment is the same as that in Embodiment 2 or Embodiment 1.

本实施例提供一种低耗能的低碳烃水蒸汽重整制氢的工艺,以某次运行(产能:2×104Nm3/h)为例,本实施例的工艺是在实施例2的基础上减少原料耗量,提高蒸汽碳比,同时调整燃料气用量。This embodiment provides a low-energy low-carbon hydrocarbon steam reforming hydrogen production process. Taking a certain operation (capacity: 2×10 4 Nm 3 /h) as an example, the process of this embodiment reduces the raw material consumption, improves the steam-carbon ratio, and adjusts the fuel gas consumption on the basis of Embodiment 2.

与实施例2相比,本实施例的关键的工艺参数如下:Compared with Example 2, the key process parameters of this embodiment are as follows:

1)原料丙烷(14.9t/h、35℃、1.5MPa、液态)经原料增压泵20增压至5.3MPa,耗功44.07kW。1) Raw material propane (14.9 t/h, 35° C., 1.5 MPa, liquid) is pressurized to 5.3 MPa by raw material booster pump 20, consuming 44.07 kW of power.

2)控制催化重整制氢反应的反应压力为4.8MPa,转化炉5中的炉管的蒸汽碳比3.5,转化炉出口的转化气(温度:860℃、压力:4.64Mpa,H2含量67.9%,CO含量13%,干基)。2) Control the reaction pressure of the catalytic reforming hydrogen production reaction to be 4.8 MPa, the steam-to-carbon ratio of the furnace tube in the reformer 5 to be 3.5, and the reformed gas at the reformer outlet (temperature: 860°C, pressure: 4.64 MPa, H2 content 67.9%, CO content 13%, dry basis).

3)膨胀透平回收的能源为4930.1kW,透平~供电系统22的出口气体778.2℃、2.84MPa,在余热锅炉系统的余锅汽水分离19产5.0MPa饱和蒸汽(91t/h),其中,3.6t/h用于加热原料,87.4t/h用于被转化炉5的蒸汽过热段503的烟气加热至430℃,得到过热蒸汽。3) The energy recovered by the expansion turbine is 4930.1kW, the outlet gas of the turbine-power supply system 22 is 778.2℃ and 2.84MPa, and 5.0MPa saturated steam (91t/h) is produced in the waste heat boiler system's steam-water separation 19, of which 3.6t/h is used to heat the raw materials, and 87.4t/h is used to heat the flue gas of the steam superheating section 503 of the converter 5 to 430℃ to obtain superheated steam.

4)过热蒸汽分为两部分,一部分(流量:23.4t/h)直接外输;一部分(流量:63.9t/h)用于冷却原料~过热蒸汽换热器3,得到中压蒸汽,该中压蒸汽是用于进行催化重整制氢反应;最终制得产品氢(H2纯度:99.9%、流量:2×104Nm3/h即4.54t/h)和解吸气(用于做转化炉燃料,流量:28448.2Nm3/h即38.25t/h,热值:2069.29kcal/Nm34) The superheated steam is divided into two parts, one part (flow rate: 23.4 t/h) is directly transported out; the other part (flow rate: 63.9 t/h) is used to cool the raw material-superheated steam heat exchanger 3 to obtain medium-pressure steam, which is used for catalytic reforming hydrogen production reaction; finally, product hydrogen ( H2 purity: 99.9%, flow rate: 2× 104 Nm3 /h, i.e. 4.54 t/h) and desorption gas (used as reformer fuel, flow rate: 28448.2 Nm3 /h, i.e. 38.25 t/h, calorific value: 2069.29 kcal/Nm3 ) are obtained.

5)转化炉的辅助燃料(成分:CH4,1.62t/h)。转化炉排烟150.4℃,干基含氧量3%v。转化炉的原料空气(流量:120t/h、温度:25℃)。5) Auxiliary fuel for the reformer (composition: CH 4 , 1.62 t/h). Exhaust gas from the reformer is 150.4°C, with an oxygen content of 3%v on a dry basis. Raw air for the reformer (flow rate: 120 t/h, temperature: 25°C).

6)本案例中除盐水流量51.3t/h,回用净化水36t/h,其余工艺条件基本参照实施例2。。6) In this case, the desalted water flow rate is 51.3 t/h, the recycled purified water is 36 t/h, and the other process conditions are basically the same as those in Example 2.

能耗对比Energy consumption comparison

由于对比例1和实施例3的原料中的低碳烃的来源可以是炼油厂的某个管路或产品,对比例1与实施例3的主要能耗,如表3所示。Since the source of the low-carbon hydrocarbons in the raw materials of Comparative Example 1 and Example 3 may be a pipeline or product of an oil refinery, the main energy consumption of Comparative Example 1 and Example 3 is shown in Table 3.

表3对比例1和实施例3的主要能耗参数Table 3 Main energy consumption parameters of comparative example 1 and embodiment 3

注:表3中的变化量为实施例3的量减去对比例1的量得出的;表3中的冷却水负荷是计算了变换气冷却器13和原料气压缩机1级间冷却的冷却负荷之和得出;表3中的产汽是根据余热锅炉系统产饱和蒸汽总量减去原料~过热蒸汽换热器3和去原料~饱和蒸汽换热器2的蒸汽量计算得出。除变化量外,表3中的正数表示的对系统做功或提供能源的影响因素,而负数表示系统对外做功或损失能源的影响因素。Note: The change in Table 3 is obtained by subtracting the amount of Example 3 from the amount of Comparative Example 1; the cooling water load in Table 3 is calculated by calculating the sum of the cooling loads of the conversion gas cooler 13 and the interstage cooling of the raw gas compressor 1; the steam production in Table 3 is calculated based on the total saturated steam produced by the waste heat boiler system minus the steam amount of the raw material-superheated steam heat exchanger 3 and the steam amount of the raw material-saturated steam heat exchanger 2. In addition to the change, the positive numbers in Table 3 represent the factors affecting the system's work or energy supply, while the negative numbers represent the factors affecting the system's external work or energy loss.

结合表3可知,在氢气产量和纯度相同的前提下,相较于对比例1,实施例3的能耗情况如下:It can be seen from Table 3 that, under the premise of the same hydrogen output and purity, compared with Comparative Example 1, the energy consumption of Example 3 is as follows:

1、经计算,原料增压耗功由对比例1的1349.41kW降至实施例3的44.07kW,减少1305.34kw;1. After calculation, the power consumption of raw material pressurization is reduced from 1349.41kW in comparative example 1 to 44.07kW in embodiment 3, a reduction of 1305.34kw;

2、膨胀透平做功4930.11kW(等熵效率η=75%),用于外输电网或驱动装置内其他耗电设备;2. The expansion turbine produces 4930.11 kW of work (isentropic efficiency η = 75%), which is used for external transmission to the power grid or other power-consuming equipment in the drive device;

3、制氢原料增加1.8t/h,但解吸气增产,使转化炉补燃增加0.09t/h;3. The hydrogen production raw materials increased by 1.8t/h, but the desorption gas production increased, which increased the supplementary combustion of the reformer by 0.09t/h;

4、中压产汽量增加2.2t/h。4. Medium pressure steam production increased by 2.2t/h.

5、基于GB/T50441-2016《石油化工设计能耗计算标准》取能耗指标:5.0MPa蒸汽90kgEO/t、3.5MPa蒸汽88kgEO/t、电0.22kgEO/kwh、除盐水1.0kgEO/t,并原料和燃料按低发热量折成标油(甲烷1195.2kgEO/t、丙烷1107kgEO/t)以及产氢量4.54t/h计算,装置综合能耗减少235.18kgEo/t H25. Based on GB/T50441-2016 "Petrochemical Design Energy Consumption Calculation Standard", the energy consumption indicators are: 5.0MPa steam 90kgEO/t, 3.5MPa steam 88kgEO/t, electricity 0.22kgEO/kwh, demineralized water 1.0kgEO/t, and raw materials and fuels are converted into standard oil (methane 1195.2kgEO/t, propane 1107kgEO/t) according to low calorific value and hydrogen production 4.54t/h, the comprehensive energy consumption of the device is reduced by 235.18kgEo/t H2 .

长期运行或大规模制氢的能耗折算:Energy consumption conversion for long-term operation or large-scale hydrogen production:

以产量2~5万标方产品氢(99%)的标准,并根据表1~3的相关标准折标后,对比例1、实施例1~3的总能耗分别是:6368.9kgeo/h、6009.6kgeo/h、5604.8kgeo/h、5477.3kgeo/h。Based on the standard of producing 20,000 to 50,000 cubic meters of product hydrogen (99%) and after decomposing according to the relevant standards in Tables 1 to 3, the total energy consumption of Comparative Example 1 and Examples 1 to 3 are 6368.9 kgeo/h, 6009.6 kgeo/h, 5604.8 kgeo/h, and 5477.3 kgeo/h, respectively.

与对比例1相比,实施例1~3是选用液态丙烷作为原料,不仅增压功耗较低,同时利用透平将转化气内能转化为电能,因此实施例1~3的综合能耗降低;而且,通过原料加压、利用系统中的热量将原料气化并加热至特定的反应温度、提高蒸汽碳比,在更高的反应压力条件同样实现高效率地催化重整制氢反应;还具有提高液态丙烷的利用率和需要补充燃料较少的优势。Compared with Comparative Example 1, Examples 1 to 3 use liquid propane as the raw material, which not only has lower power consumption for boosting, but also utilizes a turbine to convert the internal energy of the conversion gas into electrical energy, so the comprehensive energy consumption of Examples 1 to 3 is reduced; moreover, by pressurizing the raw material, utilizing the heat in the system to gasify the raw material and heat it to a specific reaction temperature, and increasing the steam-to-carbon ratio, a highly efficient catalytic reforming hydrogen production reaction can be achieved under higher reaction pressure conditions; it also has the advantages of increasing the utilization rate of liquid propane and requiring less supplementary fuel.

上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principles of the present invention shall be equivalent replacement methods and shall be included in the protection scope of the present invention.

Claims (10)

1.一种低能耗的低碳烃水蒸汽重整制氢的方法,其特征在于,包括以下步骤:1. A method for producing hydrogen by steam reforming low-carbon hydrocarbons with low energy consumption, which is characterized by comprising the following steps: 原料增压至3.5~5.5MPa,预加热和多级加热至340~380℃后,再与中压蒸汽混合,在转化炉进行催化重整制氢反应,得到转化气;The raw material is pressurized to 3.5~5.5MPa, preheated and multi-stage heated to 340~380°C, then mixed with medium-pressure steam, and catalytically reformed to produce hydrogen in the reformer to obtain reformed gas; 转化气经透平膨胀过程和余热锅炉回收内能和热量,在390~420℃进行中温变换反应、冷却,得到变换气;部分所述变换气作为热源用于所述预加热后,再经冷却、变压吸附,得到产品氢和解吸气;The conversion gas recovers internal energy and heat through the turbine expansion process and the waste heat boiler, and undergoes medium-temperature conversion reaction and cooling at 390 to 420°C to obtain the conversion gas; part of the conversion gas is used as a heat source for the preheating, and then cooled , pressure swing adsorption to obtain product hydrogen and desorbed gas; 其中,所述催化重整制氢反应的反应条件如下:反应压力为3.0~4.8MPa,反应温度为800~900℃;所述转化炉的热源来源于所述解吸气、补充燃料和空气燃烧反应产生的热量。Wherein, the reaction conditions of the catalytic reforming hydrogen production reaction are as follows: reaction pressure is 3.0~4.8MPa, reaction temperature is 800~900°C; the heat source of the reformer comes from the desorption gas, supplementary fuel and air combustion The heat generated by the reaction. 2.根据权利要求1所述低能耗的低碳烃水蒸汽重整制氢的方法,其特征在于:所述方法还包括:2. The method for producing hydrogen by steam reforming of low-carbon hydrocarbons with low energy consumption according to claim 1, characterized in that: the method further includes: 在与压力为4.0~5.0MPa、温度为380~430℃的中压蒸汽混合前,设置有脱硫处理;Before mixing with medium-pressure steam with a pressure of 4.0 to 5.0MPa and a temperature of 380 to 430°C, a desulfurization treatment is provided; 在中温变换反应、冷却后,得到一级变换气;所述一级变换气经一级冷却、二级冷却,得到122~132℃二级变换气;所述二级变换气作为热源用于步骤1)所述预加热后,再经冷却、变压吸附,得到产品氢和解吸气。After medium-temperature shift reaction and cooling, a first-stage shift gas is obtained; the first-stage shift gas undergoes primary cooling and secondary cooling to obtain a 122-132°C second-stage shift gas; the second-stage shift gas is used as a heat source for the step 1) After the preheating, cooling and pressure swing adsorption are performed to obtain product hydrogen and desorbed gas. 3.根据权利要求2所述低能耗的低碳烃水蒸汽重整制氢的方法,其特征在于:所述中压蒸汽的制备过程包括:3. The method for hydrogen production by steam reforming of low-carbon hydrocarbons with low energy consumption according to claim 2, characterized in that: the preparation process of the medium-pressure steam includes: 将所述冷却、一级冷却和二级冷却产生的工艺冷凝水通入酸性水汽提塔的中部;将所述冷却产生的工艺冷凝水通入在酸性水汽提塔的顶部;并在酸性水汽提塔的底部通入加热蒸汽,分离出酸性气体和纯净水;The process condensed water generated by the cooling, primary cooling and secondary cooling is passed into the middle of the acid water stripping tower; the process condensed water generated by the cooling is passed into the top of the acid water stripping tower; and in the acid water stripping tower Heating steam is introduced at the bottom of the tower to separate acid gas and pure water; 除盐水加热至100~112℃,与一部分纯净水混合,经加压,除氧水换热器、余热锅炉和转化炉的饱和水蒸发段加热至265~282℃,得到饱和蒸汽;所述饱和蒸汽经转化炉的蒸汽过热段进一步加热至400~450℃,得到过热蒸汽;所述部分过热蒸汽经一级原料换热器冷却得到中压蒸汽;The demineralized water is heated to 100-112°C, mixed with a part of pure water, and after pressurization, the deoxygenated water heat exchanger, waste heat boiler and saturated water evaporation section of the reformer are heated to 265-282°C to obtain saturated steam; the saturated water The steam is further heated to 400-450°C through the steam superheating section of the reformer to obtain superheated steam; the partially superheated steam is cooled by the primary raw material heat exchanger to obtain medium-pressure steam; 其中,所述饱和蒸汽的压力为4.0~5.0MPa;所述过热蒸汽的压力为4.0~5.0MPa;所述原料包括液态的丙烷、液态的丁烷、液态的戊烷中的至少一种;所述原料的压力为1.0MPa~1.8MPa。Wherein, the pressure of the saturated steam is 4.0-5.0MPa; the pressure of the superheated steam is 4.0-5.0MPa; the raw material includes at least one of liquid propane, liquid butane, and liquid pentane; The pressure of the raw materials is 1.0MPa~1.8MPa. 4.根据权利要求3所述低能耗的低碳烃水蒸汽重整制氢的方法,其特征在于:4. The method for producing hydrogen by steam reforming of low-carbon hydrocarbons with low energy consumption according to claim 3, characterized in that: 所述多级加热步骤包括:以部分饱和蒸汽为热源的一级加热和以部分过热蒸汽为热源的二级加热;剩余部分的饱和蒸汽用于被加热形成过热蒸汽;剩余部分过热蒸汽直接向外输送。The multi-stage heating step includes: primary heating with partially saturated steam as the heat source and secondary heating with partially superheated steam as the heat source; the remaining saturated steam is used to be heated to form superheated steam; the remaining superheated steam is directed outward. delivery. 5.根据权利要求2或3所述低能耗的低碳烃水蒸汽重整制氢的方法,其特征在于:所述原料还包括气态烷烃。5. The method for producing hydrogen by steam reforming low-carbon hydrocarbons with low energy consumption according to claim 2 or 3, characterized in that: the raw material further includes gaseous alkanes. 6.根据权利要求3或4所述低能耗的低碳烃水蒸汽重整制氢的方法,其特征在于:所述转化气的压力为3.2~4.8MPa;所述余热锅炉的入口处的转化气的压力为2.6~3.2MPa;6. The method for producing hydrogen by steam reforming of low-carbon hydrocarbons with low energy consumption according to claim 3 or 4, characterized in that: the pressure of the conversion gas is 3.2-4.8MPa; the conversion at the inlet of the waste heat boiler The gas pressure is 2.6~3.2MPa; 在所述中压蒸汽的制备过程中,所述加压具体为:将除盐水和部分所述纯净水混合、加压至5.2~6.6MPa。In the preparation process of the medium-pressure steam, the pressurization specifically includes: mixing desalted water and part of the purified water and pressurizing to 5.2-6.6MPa. 7.根据权利要求2或3所述低能耗的低碳烃水蒸汽重整制氢的方法,其特征在于:所述透平膨胀过程中的等熵效率70%~80%。7. The method for producing hydrogen by steam reforming low-carbon hydrocarbons with low energy consumption according to claim 2 or 3, characterized in that: the isentropic efficiency during the turbine expansion process is 70% to 80%. 8.根据权利要求2或3所述低能耗的低碳烃水蒸汽重整制氢的方法,其特征在于:所述产品氢和解吸气的流量之比为1:(8~9);所述产品氢的流量为4~6t/h;所述补充燃料和解吸气的流量之比为(20~180):1;所述产品氢为99.9%的氢气。8. The method for producing hydrogen by steam reforming of low-carbon hydrocarbons with low energy consumption according to claim 2 or 3, characterized in that: the flow ratio of the product hydrogen and the desorbed gas is 1: (8-9); The flow rate of the product hydrogen is 4-6t/h; the flow ratio of the supplementary fuel and desorption gas is (20-180):1; the product hydrogen is 99.9% hydrogen. 9.一种低能耗的低碳烃水蒸汽重整制氢系统,包括:一级原料换热器、二级原料换热器、脱硫反应器、转化炉、余热锅炉系统、除氧水换热器、中温变换反应器、变换气第一分液罐、热水换热器、除盐水换热器、变换气第二分液罐、变换气冷却器、变换气第三分液罐、变压吸附系统和酸性水汽提塔;所述余热锅炉系统包括余热锅炉和余锅汽水分离器;所述转化炉的燃烧室设置有空气和补充燃料的入口;9. A low-energy low-carbon hydrocarbon steam reforming hydrogen production system, including: a primary raw material heat exchanger, a secondary raw material heat exchanger, a desulfurization reactor, a reforming furnace, a waste heat boiler system, and a deoxygenated water heat exchanger. reactor, medium temperature shift reactor, first shift gas separation tank, hot water heat exchanger, demineralized water heat exchanger, second shift gas separation tank, shift gas cooler, third shift gas separation tank, pressure transformer Adsorption system and acid water stripping tower; the waste heat boiler system includes a waste heat boiler and a waste boiler steam-water separator; the combustion chamber of the reformer is provided with inlets for air and supplementary fuel; 其特征在于,It is characterized by: 还包括原料增压泵、预加热换热器、透平膨胀机、发电机和旁路阀;Also includes feedstock booster pump, preheating heat exchanger, turboexpander, generator and bypass valve; 所述原料增压泵通过管路依次与预加热换热器、一级原料换热器、二级原料换热器、脱硫反应器、转化炉、余热锅炉、中温变换反应器、除氧水换热器、变换气第一分液罐相连;The raw material boosting pump communicates with the preheating heat exchanger, primary raw material heat exchanger, secondary raw material heat exchanger, desulfurization reactor, reformer, waste heat boiler, medium temperature shift reactor, and deoxygenated water exchanger through pipelines. The heater and the first liquid separation tank of the conversion gas are connected; 所述脱硫反应器和转化炉之间的管路上设置有接入中压蒸汽的管路;The pipeline between the desulfurization reactor and the reformer is provided with a pipeline for connecting medium-pressure steam; 所述透平膨胀机和旁路阀,以并联的形式接入转化炉和余热锅炉之间的管路,用于回收利用转化气的内能和确保系统稳定运行;The turbine expander and bypass valve are connected in parallel to the pipeline between the reformer and the waste heat boiler to recycle and utilize the internal energy of the reformed gas and ensure stable operation of the system; 所述变换气第一分液罐的顶部通过管路依次与热水换热器、除盐水换热器、变换气第二分液罐相连;所述变换气第二分液罐的顶部与预加热换热器相连,再与变换气冷却器、变换气第三分液罐相连;所述变换气第三分液罐的顶部与变压吸附系统相连;所述变压吸附系统设置有产品氢的输出管路和给转化炉提供解吸气的管路;The top of the first liquid separation tank of the shift gas is connected to the hot water heat exchanger, the desalted water heat exchanger and the second liquid separation tank of the shift gas in sequence through pipelines; the top of the second liquid separation tank of the shift gas is connected to the preheated The heating heat exchanger is connected, and then connected to the shift gas cooler and the third shift gas liquid separation tank; the top of the third shift gas liquid separation tank is connected to the pressure swing adsorption system; the pressure swing adsorption system is equipped with product hydrogen The output pipeline and the pipeline that provides desorbed gas to the reformer; 所述变换气第一分液罐的底部通过管路与变换气第二分液罐的底部相连后,再与酸性水汽提塔的中部进料口相连。The bottom of the first liquid separation tank of the shift gas is connected to the bottom of the second liquid separation tank of the shift gas through a pipeline, and then connected to the middle feed port of the acid water stripping tower. 10.根据权利要求9所述低能耗的低碳烃水蒸汽重整制氢的系统,其特征在于:还包括:原料气压缩机、除氧器和除氧水增压泵;10. The low-energy consumption low-carbon hydrocarbon steam reforming hydrogen production system according to claim 9, characterized in that: it further includes: a feed gas compressor, a deaerator and a deoxygenated water booster pump; 除盐水换热器通过管路依次与除氧器、除氧水增压泵、除氧水换热器相连后,再与余热锅炉和余锅汽水分离器相连,用于给余锅汽水分离器提供饱和水;The demineralized water heat exchanger is connected to the deaerator, deoxygenated water booster pump, and deoxygenated water heat exchanger through pipelines, and then connected to the waste heat boiler and the residual boiler steam-water separator to feed the residual boiler steam-water separator. Provide saturated water; 余锅汽水分离器的底部设置有经过转化炉的饱和水蒸发段的管路,用回收利用转化炉的热量制得饱和蒸汽;The bottom of the residual boiler steam-water separator is equipped with a pipeline that passes through the saturated water evaporation section of the reformer, and the heat of the reformer is recycled to produce saturated steam; 余锅汽水分离器的顶部的管路分为两路,一路经转化炉的蒸汽过热段,用于产生过热蒸汽;一路与一级原料换热器、除氧器相连,实现回收过热蒸汽中的热量并用于原料的一级加热和除氧器的加热;所述除氧器设置有一级原料换热器的接入管路;The pipeline at the top of the residual boiler steam-water separator is divided into two lines. One line passes through the steam superheating section of the reformer to generate superheated steam; the other line is connected to the primary raw material heat exchanger and deaerator to realize the recovery of superheated steam. The heat is also used for the primary heating of the raw materials and the heating of the deaerator; the deaerator is equipped with an access pipeline to the primary raw material heat exchanger; 经过转化炉的蒸汽过热段后的管路再分为两路,一路与直接外输的管路连接,用于过热蒸汽的外送;一路与二级原料换热器相连,用于原料的二级加热。The pipeline after passing through the steam superheating section of the reformer is divided into two lines. One line is connected to the direct export pipeline for the transmission of superheated steam; the other line is connected to the secondary raw material heat exchanger for the secondary raw material heat exchanger. level heating.
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