CN104024149A - 甲醇和脲的联合生产 - Google Patents
甲醇和脲的联合生产 Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 195
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000004202 carbamide Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 18
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 76
- 239000007789 gas Substances 0.000 claims description 48
- 229910021529 ammonia Inorganic materials 0.000 claims description 37
- 235000011089 carbon dioxide Nutrition 0.000 claims description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 32
- 230000015572 biosynthetic process Effects 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000003786 synthesis reaction Methods 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 22
- 230000009466 transformation Effects 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003345 natural gas Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000003507 refrigerant Substances 0.000 claims description 4
- 235000009508 confectionery Nutrition 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000000629 steam reforming Methods 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 238000011144 upstream manufacturing Methods 0.000 claims 1
- 238000013022 venting Methods 0.000 abstract 1
- 229960004424 carbon dioxide Drugs 0.000 description 13
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 230000001131 transforming effect Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- C07C273/10—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds combined with the synthesis of ammonia
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Abstract
在不将大量二氧化碳排放至大气中的情况下从烃进料联合生产甲醇和脲的方法。
Description
本发明涉及一种由烃进料联合生产甲醇和脲的方法。更具体地,本发明涉及一种由含烃原料生产甲醇和脲产物的连续和单程(once-through)(单程(single pass))方法,借助于一级和二级转化(reforming),中间甲醇和氨形成,以及单一过程序列中氨转化为脲产物,其中过量二氧化碳和氢气的产生大量减少。
由氨和二氧化碳转化生产脲是一种公知的方法,以及通常在工业中使用。
由US专利申请No. 2010/0133472进一步已知由合成气联合生产甲醇和氨,其中过量二氧化碳和氢气的产生减少。
本发明的主要目的是提供一种由烃原料联合生产甲醇和脲的方法,其中过量二氧化碳和氢气的产生大量减少。
术语“过量二氧化碳和氢气的产生大量减少”应以这样的方式理解,烃原料向合成气的转化在为甲醇和脲的产生提供基本化学计量的合成气的条件下进行,导致仅根据从甲醇和脲的联合生产中清除惰性气体的需要而释放二氧化碳和氢气。
当在合并的蒸汽和二氧化碳一级烃转化和利用富氧空气的二级转化第二步骤中生产合成气时,实现本发明的主要目的。
因此,本发明提供一种从烃原料联合生产甲醇和脲的方法,其包括以下连续步骤:
(a) 通过在一级转化阶段和随后在二级转化阶段蒸汽转化烃原料,生产含有氢气、一氧化碳和二氧化碳以及氮气的合成气;
(b) 使来自步骤(a)的合成气经历部分水气转换;
(c) 从来自步骤(b)的合成气中去除至少部分二氧化碳;
(d) 在单程甲醇合成阶段催化转化来自步骤(c)的合成气的一氧化碳、二氧化碳和氢气,取出含有甲醇的流出物以及含有氮气、氢气和未转化的一氧化碳和二氧化碳的气态流出物;
(e) 使来自步骤(d)的气态流出物经历催化甲烷化,以去除未转化的一氧化碳和二氧化碳;
(f) 在氨合成阶段催化转化来自步骤(e)的气态流出物中的氮气和氢气,和取出含有氨的流出物;和
(g) 将至少部分含氨的流出物通至脲合成阶段,通过与从步骤(c)中的合成气去除的至少部分二氧化碳反应,使流出物中的氨转化为脲,
其中将步骤(c)中获得的一部分二氧化碳再循环至步骤(a)中的一级转化阶段,和/或其中步骤(a)中的二级转化阶段采用富氧空气操作。
如本文中使用的,术语“合成气的部分水气转换”表示一部分合成气绕过水气转换反应并在反应之后与转换的合成气合并。
如在本文中进一步使用的,术语“一级转化阶段”表示在常规蒸汽甲烷转化器(SMR),例如管状转化器中进行的转化,利用由来自燃烧器,例如沿着管状转化器壁排列的燃烧器的辐射热提供的吸热转化所需的热。
同样如在本文中使用的,术语“二级转化阶段”表示在自热式转化器或催化部分氧化反应器中进行的转化。
如在本文中进一步使用的,术语“单程的甲醇合成阶段”表示甲醇在以单程结构工作的至少一个催化反应器中产生,即甲醇合成中产生的任何气体,特别是含有氢气和未转化的氧化碳的气体流出物的体积流量并不显著再循环(不超过5%)回到甲醇合成阶段的至少一个甲醇反应器中。
用于本发明中的合适的烃原料包括甲烷、天然气、石脑油和高级烃。
优选地,烃原料包含例如天然气、液化天然气(LNG)或代用天然气(SNG)形式的甲烷。
当使用石脑油和高级烃时,优选在一级转化阶段之前使这些原料经历预转化步骤。但是,预转化可以用于所有类型的烃原料。
借助于本发明,我们直接使用控制转化、甲醇合成、氨合成和脲合成的反应,使得可以在不排放由二级转化合成气去除的二氧化碳的情况下联合生产甲醇和脲。
根据本发明的方法,来自步骤(b)的合成气中的二氧化碳和一氧化碳的量减去由步骤(c)再循环至步骤(a)的二氧化碳的量满足甲醇合成反应和脲反应中所需的化学计量的量:
CO + 2 H2 = CH3OH
CO2 + 3 H2 = CH3OH + H2O
2NH3 + CO2 = (NH2)2CO + H2O。
同时,来自步骤(a)的合成气中的氢气和氮气的量匹配上述甲醇合成反应和氨合成中所需的化学计量的量:
2N2 + 3H2 = 2NH3。
这意味着来自步骤(b)的合成气中的H2、CO、CO2的摩尔含量将满足以下关系:
M(H2) = 3*M(N2) + 2*M(CO) + 3*(M(CO2)-M(N2)-REC)
其中REC为从步骤(c)至步骤(a)的摩尔CO2再循环流量。
这在当控制一级蒸汽转化反应:
CH4 + H2O = CO + 3H2;和
CH4 + 2H2O = CO2 + 4H2
和/或随后的二级蒸汽转化中与富氧空气的部分氧化:
CH4 + 1/2O2 = CO + 2H2
和水-气转换反应:
H2O + CO = CO2 + H2时获得。
为保持最终合成气中一氧化碳,二氧化碳和氢气的所需量,可以将控制量的从该气体中去除的二氧化碳再循环至一级转化阶段来抑制转换反应,以便避免产生超出甲醇、氨和脲合成中所用的所需量的氢气和二氧化碳。
在采用富氧空气的二级转化器或自热式转化器中进行二级转化,以提供氨合成所需的氮气量和甲醇合成所需的一氧化碳、二氧化碳和氢气量,以及将二氧化碳再循环至一级转化器和将氨转化为脲所必需的二氧化碳量。
通过在步骤(c)中去除二氧化碳之前,使部分合成气经历水气转换反应,获得一氧化碳/二氧化碳比率的最终控制,所述比率满足甲醇和氨合成所需的氮气、一氧化碳、二氧化碳和氢气量,以及将二氧化碳再循环至一级转化器和将氨转化为脲所必需的二氧化碳量。
最终合成气通过上述测量调节至含有摩尔比率基本符合甲醇合成和氨合成中的化学计量量的一氧化碳、二氧化碳、氢气和氮气,以及提供用于脲合成和任选用于一级转化阶段的所需二氧化碳量。
因此,在本发明的优选实施方案中,来自步骤(b)中的部分转换的合成气中H2、CO、CO2和N2的摩尔含量满足以下关系I,精确度在10%内:
I:M(H2) = 3*M(N2) + 2*M(CO) + 3*(M(CO2)-M(N2)-REC)
其中REC为从步骤(c)至步骤(a)的摩尔CO2再循环流量。
通过将来自步骤(c)的二氧化碳再循环至步骤(a)中的一级转化阶段和/或通过用富氧空气进行步骤(a)中的二级转化阶段和/或通过部分转换来自步骤(a)的合成气,获得关系I。
本发明的方法是环境友好的,因为没有将从二级转化的合成气中去除的CO2排放进周围环境中。除少量二氧化碳在吹扫气体中被排放至环境中之外,该方法中产生的几乎所有一氧化碳(和二氧化碳)用于甲醇和脲合成。
可以如本领域中已知的,在物理或化学洗涤中用任何传统方法将二氧化碳从二级转化合成气中去除。
优选地,通过已知的Benefield法去除二氧化碳,其允许容易地回收如上所述用于脲合成和任选用于再循环至一级转化阶段的吸收的二氧化碳。
甲醇合成阶段优选由传统方法进行,使合成气在高压和高温,例如60-150巴和150-300℃下,通过包含至少一个甲醇催化剂固定床的至少一个甲醇反应器。特别优选的甲醇反应器为由合适的冷却剂,例如沸水冷却的固定床反应器,例如沸水反应器(BWR)。在一个特定实施方案中,使合成气通过一系列一个或多个沸水反应器和随后通过绝热的固定床反应器来进行步骤(d)中的甲醇合成阶段。优选地,一个或多个沸水反应器为缩合甲醇型的单反应器形式,其在普通外壳内包含甲醇催化剂颗粒固定床以及适合于用冷却剂间接冷却甲醇合成气的冷却装置,并且其优选在超过90 bar和低于150 bar,更优选超过110 bar和低于130 bar的压力下工作,如我们于2008年2月25日提交的DK专利申请PA 2008 00261和PA 2008 00260中所述的。根据这些申请,使用甲醇反应器能够在比典型地为约80至90 bar的常规沸腾反应器高的多的压力下操作。另外,其能够使用单反应器而非两个常规沸水反应器,由此显著降低装置成本。此外,因为甲醇合成阶段的操作压力可以保持高达约120 bar或甚至更高,就设备尺寸和总体投资成本而言,存在显著的节约,因为在高压下有利于甲醇合成。
因此,本发明能够在类似操作压力,例如130 bar下使甲醇和氨合成单元工作,意味着如上所述简化的方法,设备尺寸方面显著节约。也可在两个不同工作压力,例如在甲醇合成阶段为80-90 bar,在氨合成阶段为130 bar下操作,意味着节约甲醇合成阶段的能量。
在步骤(d)中,含有甲醇的排放物优选为液体排放物。这种排放物通过冷却和冷凝来自甲醇反应器的合成气来获得。因此,本发明的方法可以进一步包含冷却从每个甲醇反应器取出的合成气以冷凝甲醇,使气体通过分离器,从含有粗甲醇的分离器中取出底部馏分,取出含通过随后的甲醇反应器的合成气的塔顶馏分,以及通过合并含有粗甲醇的每个反应器的分离器的底部馏分,形成含有甲醇的单一液体排放物。
应理解如在本文中使用的,术语“甲醇反应器”包含绝热的固定床反应器和冷却的反应器,例如沸水反应器以及冷凝甲醇型反应器,其在普通外壳内包含甲醇催化剂颗粒固定床和适合于用冷却剂间接冷却甲醇合成气的冷却装置,绝热的固定床反应器。
在步骤(e)中,在至少一个甲烷化反应器中进行将一氧化碳转化为甲烷的催化甲烷化阶段,所述反应器优选为含有甲烷化催化剂固定床的绝热反应器。
在步骤(f)中,任选使含有正确比例的氢气和氮气(H2:N2摩尔比率为3:1)的来自甲烷化步骤的氨合成气通过压缩机,获得所需氨合成压力,例如120至200 bar,优选约130 bar。然后借助于氨合成回路,以常规方式产生氨,所述氨合成回路包含至少一个氨转化器,所述转化器含有至少一个氨催化剂固定床,具有夹层冷却。可以通过冷凝和随后分离,从含有氨的排放物中以液氨形式回收氨。优选地,从氨合成阶段取出含有氢气、氮气和甲烷的废气流,其也为富氢流(H2>90体积%)。这些流可以例如源自吹扫气体回收设备。优选地,例如通过与甲醇合成气体合并,将该氢气流加入到甲醇合成阶段(步骤(c))中。这种富氢流的再循环能够使方法效率更高,因为有用的氢气可用于甲醇合成和随后的氨合成中,而不是简单地用作燃料。
为了改善方法的能量效率,使步骤(e)的含有氢气、氮气和甲烷的废气流返回到步骤(a)中,即其作为废气燃料返回到装置的转化单元中,具体地返回到一次转化阶段。
然后通过与从如上所述步骤(c)回收的二氧化碳反应,将从氨合成中取出的氨转换成脲产物。
按照本发明,部分氨可以以氨产物的形式取出,其改变关系I如下:
II:M(H2) = 3*M(N2) + 2*M(CO) + 3*(M(CO2)-M(N2)+2*P-REC)
其中p为来自步骤(f)的氨产物摩尔量。
Claims (10)
1.从烃原料联合生产甲醇和脲的方法,其包括以下连续步骤:
(a) 通过在一级转化阶段和随后在二级转化阶段蒸汽转化所述烃原料,制备含有氢气,一氧化碳和二氧化碳以及氮气的合成气;
(b) 使来自步骤(a)的合成气经历部分水气转换;
(c) 从来自步骤(b)的合成气中去除至少部分二氧化碳;
(d) 在单程甲醇合成阶段催化转化来自步骤(c)的合成气的一氧化碳,二氧化碳和氢气,取出含有甲醇的流出物以及含有氮气、氢气和未转化的一氧化碳和二氧化碳的气态流出物;
(e) 使来自步骤(d)的气态流出物经历催化甲烷化,以去除未转化的一氧化碳和二氧化碳;
(f) 在氨合成阶段催化转化来自步骤(e)的气态流出物中的氮气和氢气,和取出含有氨的流出物;和
(g) 将至少部分含氨的流出物通至脲合成阶段,通过与从步骤(c)中的合成气去除的至少部分二氧化碳反应,使流出物中的氨转化为脲产物,
其中将步骤(c)中获得的二氧化碳的一部分再循环至步骤(a)中的一级转化阶段和/或其中步骤(a)中的二级转化阶段采用富氧空气操作。
2.根据权利要求1的方法,其中来自步骤(b)中的部分转换的合成气中H2、CO、CO2和N2的摩尔含量满足以下关系I,精确度在10%内:
I:M(H2) = 3*M(N2) + 2*M(CO) + 3*(M(CO2)-M(N2)-REC)
其中REC为从步骤(c)至步骤(a)的摩尔CO2再循环流量。
3.根据权利要求1或2的方法,其中所述烃原料为天然气,代用天然气(SNG),石脑油和高级烃。
4.根据权利要求1至3任一项的方法,其中将二氧化碳以获得0.0至0.43的二氧化碳对甲烷摩尔比率的量再循环到步骤(a)中的一级转化阶段。
5.根据权利要求1至4任一项的方法,其中二级转化阶段采用富氧空气进行,和其中富氧空气含有至多99.5%纯氧的环境氧气含量。
6.根据权利要求1或5任一项的方法,其中通过使合成气通过一系列一个或多个沸水反应器和随后通过绝热固定床反应器来进行步骤(d)中的甲醇合成阶段。
7.根据权利要求6的方法,其中所述一个或多个沸水反应器为冷凝甲醇型的单反应器形式,其在普通外壳内包含甲醇催化剂颗粒固定床和适合于用冷却剂间接冷却甲醇合成气的冷却装置。
8.根据权利要求6或7的方法,其进一步包括冷却从每个甲醇反应器取出的合成气以冷凝甲醇,使该气体通过分离器,从含有粗甲醇的分离器中取出底部馏分,取出含通至随后的甲醇的合成气的塔顶馏分,和通过合并含未处理甲醇的每个反应器的分离器的底部馏分形成含有甲醇的单一液体排放物。
9.根据在前权利要求任一项的方法,其中含有氢气、氮气和甲烷的废气流用作用于加热步骤(a)中的一级转化阶段的燃料。
10.根据在前权利要求任一项的方法,其中使所述烃原料经历步骤(a)上游的预转化。
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