CN104030245B - After reclaiming light olefin, in oil refinery dry gas, high receipts rate high purity carries hydrogen methods and device - Google Patents
After reclaiming light olefin, in oil refinery dry gas, high receipts rate high purity carries hydrogen methods and device Download PDFInfo
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- 239000007789 gas Substances 0.000 title claims abstract description 156
- 239000001257 hydrogen Substances 0.000 title claims abstract description 80
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 80
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title 1
- 239000012528 membrane Substances 0.000 claims abstract description 112
- 238000000926 separation method Methods 0.000 claims abstract description 105
- 238000001179 sorption measurement Methods 0.000 claims abstract description 73
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 150000002431 hydrogen Chemical class 0.000 claims description 24
- 239000012466 permeate Substances 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
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- 230000008595 infiltration Effects 0.000 claims 3
- 238000001764 infiltration Methods 0.000 claims 3
- 238000011084 recovery Methods 0.000 abstract description 23
- 238000000605 extraction Methods 0.000 abstract description 14
- 239000000567 combustion gas Substances 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000002485 combustion reaction Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000003795 desorption Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000004952 Polyamide Substances 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 239000002737 fuel gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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Abstract
回收轻烯烃后炼厂干气中高收率高纯度提氢方法，包括如下步骤：步骤1.一段膜分离；步骤2.一级变压吸附；步骤3.二级变压吸附；步骤4.二段膜分离。及回收轻烯烃后炼厂干气中高收率高纯度提氢装置，包括第一膜分离装置、第二膜分离装置、第一变压吸附塔、第二变压吸附塔和第一、第二加压装置。采用本发明所述的回收轻烯烃后炼厂干气中高收率高纯度提氢方法及装置，采用变压吸附、膜分离二者结合的技术，弥补了两种工艺各自存在的纯度和回收率低的缺陷，实现了对回收轻烯烃后的炼厂干气中氢气的高收率，高纯度的回收，回收氢气后的剩余气体可直接进入炼厂燃烧气管网燃烧。
The method for extracting hydrogen with high yield and high purity from refinery dry gas after recovering light olefins comprises the following steps: Step 1. One-stage membrane separation; Step 2. One-stage pressure swing adsorption; Step 3. Two-stage pressure swing adsorption; Step 4. Two Segment membrane separation. And the high-yield and high-purity hydrogen extraction device in the refinery dry gas after recovering light olefins, including the first membrane separation device, the second membrane separation device, the first pressure swing adsorption tower, the second pressure swing adsorption tower and the first and second pressure swing adsorption towers. Pressurization device. The high-yield and high-purity hydrogen extraction method and device in the refinery dry gas after recovering light olefins described in the present invention, and the combination of pressure swing adsorption and membrane separation technology, make up for the respective purity and recovery of the two processes With low defects, the high yield and high purity recovery of hydrogen in the dry gas of the refinery after recovery of light olefins is realized, and the remaining gas after recovery of hydrogen can directly enter the combustion gas pipeline network of the refinery for combustion.
Description
技术领域 technical field
本发明属于化工分离及化工机械领域，涉及一种回收轻烯烃后炼厂干气中高收率高纯度提氢方法及装置。 The invention belongs to the field of chemical separation and chemical machinery, and relates to a method and device for extracting hydrogen with high yield and high purity from refinery dry gas after recovering light olefins.
背景技术 Background technique
炼厂干气中的有用组分主要为氢气、轻烯烃和轻烷烃等。这些组分在炼厂中都是很有价值的，但目前它们很大量仍然没有实现最优化利用，而是直接用作了燃料，有的甚至直接点火炬放空。对于炼厂干气中占量最大的催化裂化干气，既含有氢气，还含有大量轻烯烃和轻烷烃。这些组分可以分离出来分别利用，比将其直接用作燃料或重整制氢、合成甲醇的原料效益要高。 The useful components in refinery dry gas are mainly hydrogen, light olefins and light alkanes. These components are very valuable in the refinery, but at present, a large amount of them have not been optimally utilized, but are directly used as fuel, and some are even directly ignited to vent. For the catalytic cracking dry gas, which accounts for the largest amount in the refinery dry gas, it contains not only hydrogen, but also a large amount of light olefins and light alkanes. These components can be separated and used separately, which is more beneficial than using them directly as fuel or raw materials for reforming hydrogen production and synthesizing methanol.
炼厂干气回收轻烯烃目前有多种方法，例如深冷分离等，属于得到广泛运用的现有技术，炼厂干气中轻烯烃含量通常在10-40%体积百分比，剩余气体为氢气、氮气和甲烷，虽然可以通过燃烧剩余气体获得热量，但氢气可以在炼厂中作为加氢使用，价格较高，作为燃料气燃烧的方式并不经济。在回收轻烯烃后的炼厂干气中还含有大约40-80%的氢气，经济价值不可忽略。 There are currently many methods for recovering light olefins from refinery dry gas, such as cryogenic separation, etc., which are widely used existing technologies. The content of light olefins in refinery dry gas is usually 10-40% by volume, and the remaining gas is hydrogen, Nitrogen and methane can obtain heat by burning the remaining gas, but hydrogen can be used as hydrogenation in refineries, the price is relatively high, and it is not economical to burn as fuel gas. The refinery dry gas after recovering light olefins still contains about 40-80% hydrogen, and its economic value cannot be ignored.
目前对回收轻烯烃后干气回收其中大量氢气，可以采用膜分离法、变压吸附、深冷分离等方法，但是，通过膜分离法回收的氢气纯度不高，一般为95%以下，由于纯度直接影响到氢气的价格，因此膜分离法经济价值不大。而变压吸附氢气回收率偏低，通常只有85%，深冷分离由于需要大量冷量，对氢气采用深冷分离成本过于昂贵，且深冷分离得到的氢气纯度不高。 At present, methods such as membrane separation, pressure swing adsorption, and cryogenic separation can be used to recover a large amount of hydrogen from dry gas after recovery of light olefins. However, the purity of hydrogen recovered by membrane separation is not high, generally below 95%. It directly affects the price of hydrogen, so the membrane separation method has little economic value. However, the hydrogen recovery rate of pressure swing adsorption is low, usually only 85%. Because cryogenic separation requires a large amount of cooling capacity, the cost of cryogenic separation of hydrogen is too expensive, and the purity of hydrogen obtained by cryogenic separation is not high.
发明内容 Contents of the invention
为克服现有技术存在的回收率低或回收纯度低，经济效益差的技术缺陷，本发明公开一种回收轻烯烃后炼厂干气中高收率高纯度提氢方法及装置，对回收轻烯烃后的炼厂干气进行氢气回收。 In order to overcome the technical defects of low recovery rate or low recovery purity and poor economic benefits in the prior art, the present invention discloses a high-yield and high-purity hydrogen extraction method and device in refinery dry gas after recovery of light olefins. The final refinery dry gas is used for hydrogen recovery.
本发明所述回收轻烯烃后炼厂干气中高收率高纯度提氢方法，包括如下步骤： The method for extracting hydrogen with high yield and high purity from refinery dry gas after recovering light olefins of the present invention comprises the following steps:
步骤1.一段膜分离：原料气进入第一膜分离装置，渗透气进入步骤2，非渗透气与 Step 1. One-stage membrane separation: feed gas enters the first membrane separation device, permeate gas enters step 2, non-permeate gas and
后续步骤2至3的解吸气加压混合后进入步骤4； Enter step 4 after the stripping gas of subsequent steps 2 to 3 is pressurized and mixed;
步骤2.一级变压吸附：步骤1中第一膜分离装置的渗透气进入第一变压吸附塔，第 Step 2. One-stage pressure swing adsorption: the permeate gas of the first membrane separation device in step 1 enters the first pressure swing adsorption tower, and the first
一变压吸附塔的非解吸气进入步骤3，解吸气与步骤1非渗透气、后续步骤3的解吸气加压混合后进入步骤4； The non-desorbed gas of a pressure swing adsorption tower enters step 3, and the desorbed gas enters step 4 after being pressurized and mixed with the non-permeated gas of step 1 and the desorbed gas of subsequent step 3;
步骤3.二级变压吸附：步骤2中的非解吸气进入第二变压吸附塔，第二变压吸附塔 Step 3. Secondary pressure swing adsorption: the non-desorbed gas in step 2 enters the second pressure swing adsorption tower, and the second pressure swing adsorption tower
的非解吸气输出作为产品氢气，解吸气与步骤1非渗透气、步骤2解吸气混合加压后进入步骤4； The non-desorbed gas is output as the product hydrogen, and the desorbed gas is mixed with the non-permeated gas in step 1 and the desorbed gas in step 2 to enter step 4 after being mixed and pressurized;
步骤4.二段膜分离：步骤1非渗透气、步骤2、3中第一、第二变压吸附塔输出的解 Step 4. Two-stage membrane separation: the non-permeable gas in step 1, the solution output from the first and second PSA towers in steps 2 and 3
吸气经混合加压后进入第二膜分离装置，第二膜分离装置的渗透气返回到步骤1中与原料气加压混合后一起进入第一膜分离装置。 The inhaled air enters the second membrane separation device after being mixed and pressurized, and the permeate gas from the second membrane separation device returns to step 1, pressurizes and mixes with the raw material gas, and then enters the first membrane separation device together.
优选的，所述步骤4中的膜分离装置得到的非渗透气直接进入炼厂燃烧气管网。 Preferably, the non-permeate gas obtained by the membrane separation device in step 4 directly enters the combustion gas pipeline network of the refinery.
优选的，所述步骤1中原料气进入第一膜分离装置前还包括加压步骤。 Preferably, the step 1 further includes a pressurization step before the feed gas enters the first membrane separation device.
进一步的，所述步骤1中将原料气加压至1.5-3兆帕，将原料气加压至1.5-3兆帕，所述步骤4中加压至1-2兆帕。 Further, in the step 1, the raw material gas is pressurized to 1.5-3 MPa, the raw material gas is pressurized to 1.5-3 MPa, and in the step 4, the pressure is increased to 1-2 MPa.
优选的，所述步骤1至4中操作温度均为常温,所述常温为0-40摄氏度范围。 Preferably, the operating temperatures in steps 1 to 4 are normal temperature, and the normal temperature is in the range of 0-40 degrees Celsius.
本发明所述回收轻烃后炼厂干气中高收率高纯度提氢装置，包括第一膜分离装置、第二膜分离装置、第一变压吸附塔、第二变压吸附塔和第一加压装置与第二加压装置； The high-yield and high-purity hydrogen extraction device in refinery dry gas after recovering light hydrocarbons in the present invention includes a first membrane separation device, a second membrane separation device, a first pressure swing adsorption tower, a second pressure swing adsorption tower and a first pressure swing adsorption tower. The pressurizing device and the second pressurizing device;
所述第一膜分离装置的渗透侧与第一变压吸附塔的进口连接，其非渗透侧经过第二加压装置与第二膜分离装置的进口连接，所述第二膜分离装置的渗透侧和原料气通过第一加压装置混合与第一膜分离装置的进口连接，所述第一变压吸附塔的塔顶非解吸气出口与第二变压吸附塔的进口连接，其塔底解吸气经第二加压装置和第二膜分离装置的进口连接，所述第二变压吸附塔的塔顶流出产品氢气，其塔底解吸气出口通过第二加压装置与第二膜分离装置的进口连接。 The permeate side of the first membrane separation device is connected with the inlet of the first pressure swing adsorption tower, and its non-permeate side is connected with the inlet of the second membrane separation device through the second pressurizing device, and the permeate of the second membrane separation device Side and feed gas are mixed with the inlet of the first membrane separation device through the first pressurizing device, and the top non-desorbing gas outlet of the first pressure swing adsorption tower is connected with the inlet of the second pressure swing adsorption tower, and its tower The bottom desorption gas is connected through the inlet of the second pressurization device and the second membrane separation device, the tower top of the second pressure swing adsorption tower flows out the product hydrogen, and the outlet of the bottom desorption gas passes through the second pressurization device and the second membrane separation device. The inlet connection of the two membrane separation devices.
优选的，所述第二膜分离装置的非渗透侧出口与炼厂燃烧气管网连接。 Preferably, the outlet of the non-permeate side of the second membrane separation device is connected to the refinery combustion gas pipeline network.
采用本发明所述的回收轻烯烃后炼厂干气中高收率高纯度提氢方法及装置，采用二段 The high-yield and high-purity hydrogen extraction method and device in refinery dry gas after recovering light olefins described in the present invention adopt the second stage
变压吸附、二段膜分离二者结合的技术，弥补了两种工艺各自存在的纯度和回收率低的缺陷，实现了对回收轻烯烃后的炼厂干气中氢气的高收率，高纯度的回收，回收氢气后的剩余气体可直接进入炼厂燃烧气管网燃烧。 The combination of pressure swing adsorption and two-stage membrane separation technology makes up for the defects of low purity and recovery of the two processes, and realizes the high yield of hydrogen in the dry gas of the refinery after the recovery of light olefins. The recovery of purity, the remaining gas after hydrogen recovery can be directly burned in the combustion gas pipeline network of the refinery.
附图说明 Description of drawings
图1示出本发明所述回收轻烯烃后炼厂干气中高收率高纯度提氢方法的一种具体实施方式示意图； Fig. 1 shows a schematic diagram of a specific embodiment of the high-yield and high-purity hydrogen extraction method in refinery dry gas after recovering light olefins according to the present invention;
图2示出本发明所述回收轻烯烃后炼厂干气中高收率高纯度提氢装置的一种具体实施方式示意图； Figure 2 shows a schematic diagram of a specific embodiment of a high-yield and high-purity hydrogen extraction device in refinery dry gas after recovering light olefins according to the present invention;
各图中附图标记名称为：1-第一加压装置2-第二加压装置3-第一变压吸附塔4-第二变压吸附塔5-第一膜分离装置6-第二膜分离装置7-炼厂燃烧气管网。 The names of reference signs in each figure are: 1-first pressurizing device 2-second pressurizing device 3-first pressure swing adsorption tower 4-second pressure swing adsorption tower 5-first membrane separation device 6-second Membrane separation unit 7 - refinery combustion gas pipeline network.
具体实施方式 detailed description
下面结合附图，对本发明的具体实施方式作进一步的详细说明。 The specific embodiment of the present invention will be further described in detail below in conjunction with the accompanying drawings.
现有技术中，对炼厂干气中的甲烷、乙烯、乙烷等轻烯烃回收后，剩余的气体的主要成分为大约30-60%H2、5-15%N2、5-24%甲烷、其余组分合计不超过1%，本说明书中的百分含量均为体积百分比。 In the prior art, after recovering light olefins such as methane, ethylene, and ethane in the dry gas of the refinery, the main components of the remaining gas are about 30-60% H2, 5-15% N2, 5-24% methane, The total of the remaining components does not exceed 1%, and the percentages in this description are all volume percentages.
回收轻烯烃后的炼厂干气中氢气组分最大，其次是甲烷，氢气作为常用的炼油加氢，而作为燃烧气直接燃烧非常可惜，本发明为此提供一种回收轻烯烃后炼厂干气中高收率高纯度提氢方法，包括如下步骤：步骤1.一段膜分离：原料气进入第一膜分离 The hydrogen component in the refinery dry gas after recovery of light olefins is the largest, followed by methane. Hydrogen is commonly used in oil refining hydrogenation, but it is a pity that it is directly burned as combustion gas. Therefore, the present invention provides a refinery dry gas after recovery of light olefins. The high-yield and high-purity hydrogen extraction method in gas includes the following steps: Step 1. One-stage membrane separation: raw material gas enters the first membrane separation
装置，渗透气进入步骤2，非渗透气与后续二步骤的解吸气加压混合后进入步骤4；步骤2.一级变压吸附：步骤1中第一膜分离装置的渗透气进入第一变压吸附塔，第一变压吸附塔的非解吸气进入步骤3，解吸气与步骤1非渗透气、后续一步骤的解吸气加压混合后进入步骤4；步骤3.二级变压吸附：步骤2中的非解吸气进入第二变压吸附塔，第二变压吸附塔的非解吸气输出作为产品氢气，解吸气与步骤1非渗透气、步骤2解吸气混合加压后进入步骤4；步骤4.二段膜分离：步骤1非渗透气、步骤2、3中第一、第二变压吸附塔输出的解吸气经混合加压后进入第二膜分离装置，第二膜分离装置的渗透气返回到步骤1中与原料气加压混合后一起进入第一膜分离装置。 device, the permeate gas enters step 2, and the non-permeate gas is pressurized and mixed with the desorbed gas of the subsequent two steps to enter step 4; step 2. One-stage pressure swing adsorption: the permeate gas of the first membrane separation device in step 1 enters the first Pressure swing adsorption tower, the non-desorbed gas of the first pressure swing adsorption tower enters step 3, and the desorbed gas enters step 4 after being pressurized and mixed with the non-permeated gas of step 1 and the desorbed gas of the subsequent step; step 3. Secondary Pressure swing adsorption: the non-desorbed gas in step 2 enters the second pressure swing adsorption tower, and the non-desorbed gas of the second pressure swing adsorption tower is output as product hydrogen. The desorbed gas is the same as the non-permeable gas in step 1 and desorbed in step 2 After the gas is mixed and pressurized, it enters step 4; step 4. Second-stage membrane separation: the non-permeable gas in step 1, and the desorbed gas output from the first and second PSA towers in steps 2 and 3 enter the second stage after being mixed and pressurized. Membrane separation device, the permeate gas from the second membrane separation device is returned to step 1, pressurized and mixed with raw material gas, and then enters the first membrane separation device together.
回收轻烯烃后的炼厂干气作为原料气进入第一膜分离装置对氢气进行第一次膜分离，第一膜分离装置优选为聚亚酰胺膜，分离后的渗透气中，氢气纯度被提升至60%-80% Refinery dry gas after recovering light olefins enters the first membrane separation device as raw material gas for the first membrane separation of hydrogen. The first membrane separation device is preferably a polyimide membrane, and the purity of hydrogen in the separated permeate gas is improved. to 60%-80%
，仍含有少量的甲烷和氮气，第一膜分离装置的渗透气进入第一变压吸附塔对氢气进行进一步提纯，其非渗透气仍然含有较多的氢气，经与第一、第二变压吸附塔解吸气混合加压后进入第二膜分离装置继续浓缩氢气；第一变压吸附塔得到的非解吸气进入第二变压吸附塔，解吸气则与第一膜分离装置的非渗透气、第二变压吸附塔解吸气混合加压后进入第二膜分离装置继续浓缩氢气，以提高氢气的回收率。第二变压吸附塔吸收第一变压吸附塔的非解吸气后，从第二变压吸附塔的非解吸气出口处直接输出高纯度的氢气作为产品氢气，第二变压吸附塔输出的解吸气经与第一膜装置的非渗透气、第一变压吸附塔解吸气混合加压后进入第二膜分离装置，此时第二变压吸附塔输出的解吸气中仍然含有大约6-15%的氢气组分，为进一步提高氢气收率，将这些气体经过加压后进入第二膜分离装置进行分离，第二膜分离装置优选的为聚酯膜，对其中的氢气组分纯度提高后与原料气混合加压后一起进入第一膜分离装置重复对氢气组分的回收。 , still contains a small amount of methane and nitrogen, the permeate gas from the first membrane separation unit enters the first pressure swing adsorption tower to further purify the hydrogen, and the non-permeate gas still contains more hydrogen, after being combined with the first and second pressure swing The desorbed gas from the adsorption tower is mixed and pressurized and enters the second membrane separation device to continue to concentrate hydrogen; the non-desorbed gas obtained from the first pressure swing adsorption tower enters the second pressure swing adsorption tower, and the desorbed gas is combined with the first membrane separation device. The non-permeable gas and the desorbed gas of the second pressure swing adsorption tower are mixed and pressurized, and then enter the second membrane separation device to continue to concentrate hydrogen, so as to improve the recovery rate of hydrogen. After the second pressure swing adsorption tower absorbs the non-desorption gas of the first pressure swing adsorption tower, high-purity hydrogen is directly output from the non-desorption gas outlet of the second pressure swing adsorption tower as product hydrogen, and the second pressure swing adsorption tower The output desorption gas enters the second membrane separation device after being mixed with the non-permeable gas of the first membrane device and the desorption gas of the first pressure swing adsorption tower, and then enters the second membrane separation device. Still contain about 6-15% of the hydrogen component, in order to further improve the yield of hydrogen, these gases enter the second membrane separation device after pressurization for separation, the second membrane separation device is preferably a polyester membrane, and the After the purity of the hydrogen component is improved, it is mixed with the feed gas and pressurized, and then enters the first membrane separation device to repeat the recovery of the hydrogen component.
本发明采用膜分离+二段变压吸附+膜分离的组合方式，对回收轻烯烃后的炼厂干气中的氢气组分进行回收，利用膜分离与变压吸附的组合方式，一级膜分离非渗透气、两级变压吸附塔的解吸气都重新回到系统中参与循环吸收，对氢气进行多次提纯和循环提浓氢气方式，提高了氢气的收率及纯度。 The present invention adopts the combination of membrane separation + two-stage pressure swing adsorption + membrane separation to recover the hydrogen component in the refinery dry gas after recovering light olefins, and utilizes the combination of membrane separation and pressure swing adsorption. The separation of non-permeable gas and the desorption gas of the two-stage pressure swing adsorption tower are all returned to the system to participate in the cycle absorption, and the hydrogen is purified multiple times and the cycle enriches the hydrogen, which improves the yield and purity of hydrogen.
优选的，所述步骤4中的膜分离装置得到的非渗透气由于氢气已被大部分吸收，剩余气体为甲烷为主，还含有部分氮气及轻烃的气体，热值较高，可以直接进入炼厂燃烧气管网，作为炼厂燃料气使用。 Preferably, the non-permeable gas obtained by the membrane separation device in the step 4 has been mostly absorbed by hydrogen, and the remaining gas is mainly methane, and also contains part of nitrogen and light hydrocarbon gas, which has a high calorific value and can directly enter The refinery combustion gas pipeline network is used as refinery fuel gas.
回收轻烯烃后的干气一般都自带较大压力，可以无需加压，但如果干气由于膨胀制 The dry gas after recovery of light olefins generally has a relatively high pressure, and it is not necessary to pressurize, but if the dry gas is compressed due to expansion
冷等方式已被减压的话，可以在原料气进入第一膜分离装置之前进行加压，加压范围可以选择在1.5至3兆帕，第一膜分离装置输出带压的非渗透气，与第一、第二变压吸附塔输出的解吸气混合加压后进入第二膜分离装置时的加压范围可以选择在1-2兆帕，对后续膜分离渗透效果较好。由于整个分离过程中，无论膜分离还是变压吸附对温度都无苛刻要求，可以在常温下进行，无须加热或制冷，节约了能源和设备。图1中示出本发明一种具体实施方式，包括了上述加压步骤以及将第二膜分离装置的非渗透气送入炼厂燃气管网的步骤。 If the cold and other methods have been decompressed, it can be pressurized before the feed gas enters the first membrane separation device. The pressure range can be selected from 1.5 to 3 MPa. The first membrane separation device outputs the non-permeable gas with pressure, and The desorption gas output from the first and second pressure swing adsorption towers is mixed and pressurized, and the pressure range when entering the second membrane separation device can be selected at 1-2 MPa, which has a better effect on subsequent membrane separation and permeation. Since the whole separation process, no matter membrane separation or pressure swing adsorption has no strict requirements on temperature, it can be carried out at normal temperature without heating or cooling, which saves energy and equipment. Figure 1 shows a specific embodiment of the present invention, which includes the above pressurization step and the step of sending the non-permeate gas from the second membrane separation device into the gas pipeline network of the refinery.
为实现上述方法，本发明提供一种回收轻烯烃后炼厂干气中高收率高纯度提氢装置，如图2所示，包括第一膜分离装置5、第二膜分离装置6、第一变压吸附塔3、第二变压吸附塔4和第一加压装置2；所述第一膜分离装置5、第二膜分离装置6的渗透侧都与第一变压吸附塔3的进口连接，所述第一变压吸附塔3的塔顶非解吸气出口和塔底解吸气出口分别与第二变压吸附塔4和第一膜分离装置5的进口连接，所述第二变压吸附塔4的塔底解吸气出口通过第一加压装置2与第二膜分离装置6的进口连接。第一膜分离装置为高压透氢的膜，例如聚酰胺氢膜，第二膜分离装置为低压透氢膜，例如聚碳酸酯氢膜。 In order to realize the above method, the present invention provides a high-yield and high-purity hydrogen extraction device in refinery dry gas after recovering light olefins, as shown in Figure 2, comprising a first membrane separation device 5, a second membrane separation device 6, a first Pressure swing adsorption tower 3, the second pressure swing adsorption tower 4 and the first pressurizing device 2; connected, the top non-desorbing gas outlet of the first pressure swing adsorption tower 3 and the tower bottom desorbing gas outlet are respectively connected with the inlet of the second pressure swing adsorption tower 4 and the first membrane separation device 5, and the second The bottom desorption gas outlet of the pressure swing adsorption tower 4 is connected to the inlet of the second membrane separation device 6 through the first pressurizing device 2 . The first membrane separation device is a high-pressure hydrogen-permeable membrane, such as a polyamide hydrogen membrane, and the second membrane separation device is a low-pressure hydrogen-permeable membrane, such as a polycarbonate hydrogen membrane.
回收轻烯烃后炼厂干气中高收率高纯度提氢装置，优选的，所述第一膜分离装置和第二膜分离装置的非渗透侧出口都与炼厂燃烧气管网7连接。 The high-yield and high-purity hydrogen extraction device in the refinery dry gas after recovering light olefins, preferably, both the non-permeation side outlets of the first membrane separation device and the second membrane separation device are connected to the refinery combustion gas pipeline network 7 .
为实现前述的优选加压步骤，所述第一膜分离装置的进口还连接有第二加压装置1。 In order to realize the aforementioned preferred pressurization step, the inlet of the first membrane separation device is also connected with a second pressurization device 1 .
以下给出本发明的若干具体实施例： Provide some specific embodiments of the present invention below:
实施例1.原料气含氢气40%，甲烷50%，氮气和其余气体10%，压力1.5兆帕，温度30摄氏度，以10,000Nm3/h流量送入如图2所示的装置中，原料气经过第一加压装置加压至3兆帕，进入第一膜分离装置，其中第一膜分离装置采用聚酰胺膜组件，第一变压吸附塔填装有活性炭及氧化铝等吸附剂为主，第二变压吸附塔填装有精提氢气的分子筛吸附剂为主，第二膜分离装置采用聚碳酸酯膜组件，第二加压装置对第二变压吸附塔的解吸气加压至2兆帕； Embodiment 1. raw material gas contains hydrogen 40%, methane 50%, nitrogen and other gases 10%, pressure 1.5 MPa, temperature 30 degrees Celsius, send in the device as shown in Figure 2 with 10,000Nm 3 /h flow rate, raw material The gas is pressurized to 3 MPa through the first pressurizing device and enters the first membrane separation device, wherein the first membrane separation device adopts polyamide membrane modules, and the first pressure swing adsorption tower is filled with adsorbents such as activated carbon and alumina. Mainly, the second pressure swing adsorption tower is mainly filled with molecular sieve adsorbents for refined hydrogen extraction, the second membrane separation device adopts polycarbonate membrane modules, and the second pressurization device pressurizes the desorption gas of the second pressure swing adsorption tower Pressure to 2 MPa;
测量得出对氢气的回收率为99%，回收氢气纯度为99.99%以上。 It is measured that the recovery rate of hydrogen is 99%, and the purity of recovered hydrogen is above 99.99%.
实施例2.原料气含氢气60%，甲烷25%，氮气和其余气体15%，压力2.5兆帕，温度30摄氏度，以10,000Nm3/h流量送入如图2所示的装置中，原料气直接进入第一膜分离装置，其中第一膜分离装置采用聚酰胺膜组件，第一变压吸附塔填装有活性炭及氧化铝等吸附剂为主，第二变压吸附塔填装有精提氢气的分子筛吸附剂为主，第二膜分离装置采用聚碳酸酯膜组件，第二加压装置对第二变压吸附塔的解吸气加压至1.2兆帕； Embodiment 2. raw material gas contains hydrogen 60%, methane 25%, nitrogen and other gases 15%, pressure 2.5 MPa, temperature 30 degrees Celsius, send in the device as shown in Figure 2 with 10,000Nm 3 /h flow rate, raw material The gas directly enters the first membrane separation device, wherein the first membrane separation device adopts polyamide membrane modules, the first pressure swing adsorption tower is mainly filled with adsorbents such as activated carbon and alumina, and the second pressure swing adsorption tower is filled with refined The molecular sieve adsorbent for hydrogen extraction is mainly used, the second membrane separation device adopts polycarbonate membrane modules, and the second pressurization device pressurizes the desorption gas of the second pressure swing adsorption tower to 1.2 MPa;
测量得出对氢气的回收率为99%，回收氢气纯度为99.99%以上。 It is measured that the recovery rate of hydrogen is 99%, and the purity of recovered hydrogen is above 99.99%.
实施例3.原料气含氢气75%，甲烷20%，氮气和其余气体5%，压力1兆帕，温度25摄氏度，以10,000Nm3/h流量送入如图2所示的装置中，原料气经过第一加压装置加压至3兆帕，进入第一膜分离装置，其中第一膜分离装置采用聚酰胺膜组件，第一变压吸附塔填装有活性炭及氧化铝等吸附剂为主，第二变压吸附塔填装有精提氢气的分子筛吸附剂为主，第二膜分离装置采用聚碳酸酯膜组件，第二加压装置对第二变压吸附塔的解吸气加压至1兆帕； Embodiment 3. The raw material gas contains 75% hydrogen, 20% methane, 5% nitrogen and other gases, the pressure is 1 MPa, and the temperature is 25 degrees Celsius. It is sent into the device shown in Figure 2 with a flow rate of 10,000Nm 3 /h. The gas is pressurized to 3 MPa through the first pressurizing device and enters the first membrane separation device, wherein the first membrane separation device adopts polyamide membrane modules, and the first pressure swing adsorption tower is filled with adsorbents such as activated carbon and alumina. Mainly, the second pressure swing adsorption tower is mainly filled with molecular sieve adsorbents for refined hydrogen extraction, the second membrane separation device adopts polycarbonate membrane modules, and the second pressurization device pressurizes the desorption gas of the second pressure swing adsorption tower Pressure to 1 MPa;
测量得出对氢气的回收率为99%，回收氢气纯度为99.99%以上。 It is measured that the recovery rate of hydrogen is 99%, and the purity of recovered hydrogen is above 99.99%.
实施例4.原料气含氢气80%，甲烷10%，氮气和其余气体10%，压力2兆帕，温度25摄氏度，以10,000Nm3/h流量送入如图2所示的装置中，原料气直接进入第一膜分离装置，其中第一膜分离装置采用聚酰胺膜组件，第一变压吸附塔填装有活性炭及氧化铝等吸附剂为主，第二变压吸附塔填装有精提氢气的分子筛吸附剂为主，第二膜分离装置采用聚碳酸酯膜组件，第二加压装置对第二变压吸附塔的解吸气加压至1.5兆帕； Embodiment 4. The raw material gas contains 80% hydrogen, 10% methane, 10% nitrogen and other gases, the pressure is 2 MPa, and the temperature is 25 degrees Celsius. It is sent into the device shown in Figure 2 with a flow rate of 10,000Nm 3 /h. The gas directly enters the first membrane separation device, wherein the first membrane separation device adopts polyamide membrane modules, the first pressure swing adsorption tower is mainly filled with adsorbents such as activated carbon and alumina, and the second pressure swing adsorption tower is filled with refined Molecular sieve adsorbent for hydrogen extraction is mainly used, the second membrane separation device adopts polycarbonate membrane modules, and the second pressurization device pressurizes the desorption gas of the second pressure swing adsorption tower to 1.5 MPa;
测量得出对氢气的回收率为99%，回收氢气纯度为99.99%以上。 It is measured that the recovery rate of hydrogen is 99%, and the purity of recovered hydrogen is above 99.99%.
前文所述的为本发明的各个优选实施例，各个优选实施例中的优选实施方式如果不是明显自相矛盾或以某一优选实施方式为前提，各个优选实施方式都可以任意叠加组合使用，所述实施例以及实施例中的具体参数仅是为了清楚表述发明人的发明验证过程，并非用以限制本发明的专利保护范围，本发明的专利保护范围仍然以其权利要求书为准，凡是运用本发明的说明书及附图内容所作的等同结构变化，同理均应包含在本发明的保护范围内。 The foregoing are various preferred embodiments of the present invention. If the preferred implementations in each preferred embodiment are not obviously self-contradictory or based on a certain preferred implementation, each preferred implementation can be used in any superposition and combination. The above examples and the specific parameters in the examples are only for clearly expressing the inventor's invention verification process, and are not used to limit the scope of patent protection of the present invention. The scope of patent protection of the present invention is still subject to its claims. The equivalent structural changes made in the specification and drawings of the present invention should be included in the protection scope of the present invention in the same way.
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