CN113460978B - 一种兰炭炉生产氢气、氮气、一氧化碳的方法 - Google Patents
一种兰炭炉生产氢气、氮气、一氧化碳的方法 Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000000571 coke Substances 0.000 title claims abstract description 44
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 29
- 239000001257 hydrogen Substances 0.000 title claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title description 4
- 239000007789 gas Substances 0.000 claims abstract description 98
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000002485 combustion reaction Methods 0.000 claims abstract description 32
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 26
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000003795 desorption Methods 0.000 claims abstract description 9
- 229910052786 argon Inorganic materials 0.000 claims abstract description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 9
- 238000000034 method Methods 0.000 claims description 29
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- 239000003463 adsorbent Substances 0.000 claims description 9
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002737 fuel gas Substances 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 6
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- 238000002789 length control Methods 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 description 16
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- 239000003245 coal Substances 0.000 description 7
- 239000003949 liquefied natural gas Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
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- 238000000746 purification Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010017472 Fumbling Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种兰炭炉生产氢气、一氧化碳、氮气的方法，所述方法为将兰炭尾气分离液体物质后得到原料气，采用工作压力‑0.05~0.1MPa变压吸附分离原料气，吸附塔低压解吸端获得水、二氧化碳、不饱和烃类、酚类气体、C2 +、甲烷为循环气，吸附塔高压端获得氢气、氩气、氧气、氮气、一氧化碳为产品气，将循环气送入兰炭燃烧室作为燃料，同时送入富氧空气作为助燃剂，生产得到氢气、一氧化碳、氮气。本申请通过在较低压力下分离原料气，有效降低能耗，通过准确控制燃料气中的二氧化碳与水实现兰炭炉燃烧室火焰长度控制与温度分布均匀，本申请能够有效减少气体废弃物排放、降低资源消耗。
Description
技术领域
本发明属于涉及冶金、节能、环保领域，具体涉及一种有效减少气体废弃物排放、降低资源消耗的兰炭炉生产氢气、氮气、一氧化碳的方法。
背景技术
中国天辰工程有限公司张宝珠等CN108977244A公告了一种富氧改性兰炭尾气制备液化天然气的方法。首先利用富氧气体对兰炭尾气进行富氧改性，经湿法脱硫后增压，然后预净化脱除改性兰炭尾气中的焦油、萘、苯；接力增压后变换精脱硫进行甲烷化反应，得到合成气；对合成气依次脱碳、干燥脱水、深冷液化，最终制得液化天然气。预净化及深冷液化所得再生气混合后可作为锅炉房燃料气。兰炭尾气富氧化改性后，降低氮气的含量，提高尾气中CH4，CO，CO2对后续合成甲烷化有利的组分含量，进一步降低整个LNG生产过程中的能耗，具有更高的经济效益。制备过程中能量循环利用，既能减少废气排放，又能充分利用装置自身的能量与热量，节能环保，具有很高的环境效益及经济效益。
何巨堂CN103074133A公开了一种内热式煤干馏过程外排煤气加工方法，基于以CO2为燃烧过程控温组分的煤炭化工艺，煤干馏过程使用的氧化剂是富氧气和CO2气的混合物，外排煤气主要由H2、CO、CH4、CO2、H2O等组成，该煤气经过脱CO2过程成为第一脱碳气TT1Q，使用第一脱碳气TT1Q联产H2和LNG，H2供煤焦油加氢过程使用，从而构成内热式制兰炭、焦油加氢、煤气制H2和LNG组合工艺。由于制取LNG的过程同时就是提纯H2的过程，该过程具备高度的经济性，特别适合于内热式干馏制兰炭、焦油加氢、煤气联产H2和LNG的组合过程。二氧化碳作为调节炉气温度是一个很好的想法，但是其作为氧化剂的思路却难以执行。
西安建筑科技大学赵俊学等CN101250419B公告了煤气内热低温干馏方法，将富氧或纯氧在炉外燃烧器中与燃烧煤气产生高温废气，作为煤干馏所需基础热源；将产生的高温废气通过和干馏过程产生的脱除焦油后的冷煤气混合，配制成温度为680-810℃的高温循环气；将高温循环气鼓入内热式煤干馏炉，对炉内的煤进行无氧化或弱氧化加热，实现循环部分煤气的无燃烧循环。使用该方法能够有效降低煤气中的氮含量，提高煤气的热值，提高焦油收率，改善兰炭质量。但采用富氧条件煤干馏过程中的燃烧不均匀及局部烧结问题也是类似工艺目前面临的最大困境，也导致兰炭炉大型化过程出现巨大困难。
根据以上发明专利可以看出，有意识的准确控制燃料气中二氧化碳与水含量来控制燃烧室的工作温度与温度均匀分布，没有引起大家的重视。
变压吸附气体分离技术是一种常用技术，但-0.05~0.1MPa的低压环境实现兰炭尾气分离氢气、氮气、一氧化碳是很困难的，通常工艺都是在较高压力下实现分离，能耗成本较大，发明人发明了专门的吸附剂来实现低压低成本分离。
富氧作为助燃剂，用高热值燃料直接燃烧，容易让燃烧流道温度分布不均匀，甚至出现烧结现象，准确控制燃料气中的二氧化碳与水可以实现兰炭炉燃烧室火焰长度控制与温度分布相对均匀，则是发明人经过长时间的摸索才发现的，特发明以下方法来获得氢气、一氧化碳、氮气混合气体。
发明内容
利用兰炭炉生产氢气、一氧化碳、氮气的方法，将兰炭尾气分离液体物质（包括冷却、回收焦油与苯类、脱除硫化物等过程）后称为原料气。对于采用常见工艺与活性炭及硅胶吸附剂，分离原料气高浓度二氧化碳将能耗巨大，得不偿失。采用专用的吸附剂与采用工作压力-0.05~0.1MPa变压吸附分离原料气，将大大降低操作能耗。吸附塔低压端获得两种解吸气，其一为高浓水、二氧化碳称为第一循环气，其二为二氧化碳、不饱和烃类、酚类气体、C2 +、甲烷称为第二循环气，吸附塔高压端获得氢气、氩气、氧气、氮气、一氧化碳称为产品气，将部分第一循环气与全部第二循环气送入兰炭燃烧室作为燃料，同时送入50~100%的富氧空气作为助燃剂，生产的氢气、一氧化碳、氮气用于化工原料气；为了保证燃烧室火焰长度符合兰炭炉加热均匀要求，在燃料气中的二氧化碳和水的浓度总和控制在37~57%。
富氧空气作为助燃剂，用高热值燃料掺混二氧化碳与水蒸气，可以让燃烧流道温度分布均匀，避免出现烧结现象。
具体实施方式
下面结合实施例对本发明作进一步的说明，但不以任何方式对本发明加以限制，基于本发明教导所作的任何变换或替换，均属于本发明的保护范围。
本发明兰炭炉生产氢气、一氧化碳、氮气的方法，具体为将兰炭尾气分离液体物质后得到原料气，采用工作压力-0.05~0.1MPa变压吸附分离原料气，吸附塔低压解吸端获得水、二氧化碳、不饱和烃类、酚类气体、C2+、甲烷为循环气，吸附塔高压端获得氢气、氩气、氧气、氮气、一氧化碳为产品气，将循环气送入兰炭燃烧室作为燃料，同时送入富氧空气作为助燃剂，生产得到氢气、一氧化碳、氮气。
进一步的，所述分离液体物质包括冷却、回收焦油与苯类、脱除硫化物。
进一步的，所述变压吸附使用碳分子筛为吸附剂。
进一步的，所述变压吸附使用硅铝比为10:1以上的高硅铝比分子筛为吸附剂。
进一步的，所述燃烧室中的二氧化碳和水的浓度总和控制在37~57%。
进一步的，所述生产得到的氢气、一氧化碳、氮气可用作化工合成原料气。
实施例1：单孔兰炭炉年产能7.5万吨合计产能60万吨兰炭生产线，生产氢气、一氧化碳、氮气的方法，将兰炭尾气分离液体物质（包括冷却、回收焦油与苯类、脱除硫化物等过程）后称为原料气，采用硅铝比为10:1的高硅铝比分子筛为吸附剂与采用工作压力-0.05~0.05MPa变压吸附分离原料气。吸附塔低压解吸端获得高浓水、二氧化碳为第一循环气，二氧化碳、不饱和烃类、酚类气体、C2 +、甲烷称为第二循环气，吸附塔高压端获得氢气、氩气、氧气、氮气、一氧化碳称为产品气，将70%第一循环气与全部第二循环气送入兰炭燃烧室作为燃料，同时送入50%的富氧空气作为助燃剂，生产的氢气、一氧化碳、氮气用于氨合成原料气；为了保证燃烧室火焰长度符合兰炭炉加热均匀要求，在燃料气中的二氧化碳和水的浓度总和控制在37%。
实施例2：单孔兰炭炉年产能8万吨合计产能64万吨兰炭生产线，生产氢气、一氧化碳、氮气的方法，将兰炭尾气分离液体物质（包括冷却、回收焦油与苯类、脱除硫化物等过程）后称为原料气，采用硅铝比为15:1的高硅铝比分子筛为吸附剂与采用工作压力-0.05~0.10MPa变压吸附分离原料气。吸附塔低压解吸端获得高浓水、二氧化碳为第一循环气，二氧化碳、不饱和烃类、酚类气体、C2 +、甲烷称为第二循环气，吸附塔高压端获得氢气、氩气、氧气、氮气、一氧化碳称为产品气，将40%第一循环气与全部第二循环气送入兰炭燃烧室作为燃料，同时送入85%的富氧空气作为助燃剂，生产的氢气、一氧化碳、氮气用于甲醇与氨合成原料气；为了保证燃烧室火焰长度符合兰炭炉加热均匀要求，在燃料气中的二氧化碳和水的浓度总和控制在41%。
实施例3：单孔兰炭炉年产能10万吨合计产能80万吨兰炭生产线，生产氢气、一氧化碳、氮气的方法，将兰炭尾气分离液体物质（包括冷却、回收焦油与苯类、脱除硫化物等过程）后称为原料气，采用硅铝比为20:1的高硅铝比分子筛为吸附剂与采用工作压力-0.05~0.1MPa变压吸附分离原料气。吸附塔低压解吸端获得高浓水、二氧化碳为第一循环气，二氧化碳、不饱和烃类、酚类气体、C2 +、甲烷称为第二循环气，吸附塔高压端获得氢气、氩气、氧气、氮气、一氧化碳称为产品气，将30%第一循环气与全部第二循环气送入兰炭燃烧室作为燃料，同时送入50%的富氧空气作为助燃剂，生产的氢气、一氧化碳、氮气用于甲醇与氨合成原料气；为了保证燃烧室火焰长度符合兰炭炉加热均匀要求，在燃料气中的二氧化碳和水的浓度总和控制在55%。
采用本发明，与直接使用部分兰炭尾气作燃料，部分兰炭尾气转化有机物用于化产具有投资小，节省占地与节约能耗的效果。
Claims (3)
1.一种兰炭炉生产氢气、一氧化碳、氮气的方法，其特征在于：将兰炭尾气分离液体物质后得到原料气，采用工作压力-0.05~0.1MPa变压吸附分离原料气，吸附塔低压解吸端获得水、二氧化碳、不饱和烃类、酚类气体、C2 +、甲烷为循环气，吸附塔高压端获得氢气、氩气、氧气、氮气、一氧化碳为产品气，将循环气送入兰炭燃烧室作为燃料，同时送入富氧空气作为助燃剂，所述富氧空气中氧含量为50~100%，生产得到氢气、一氧化碳、氮气；所述变压吸附使用硅铝比为10:1以上的高硅铝比分子筛为吸附剂；所述燃烧室中的二氧化碳和水的浓度总和控制在37~57%。
2.根据权利要求1所述的兰炭炉生产氢气、一氧化碳、氮气的方法，其特征在于：所述分离液体物质包括冷却、回收焦油与苯类、脱除硫化物。
3.根据权利要求1所述的兰炭炉生产氢气、一氧化碳、氮气的方法，其特征在于：所述生产得到的氢气、一氧化碳、氮气可用作化工合成原料气。
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