CN104024193A - 制备高级醇的方法 - Google Patents
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- 150000001298 alcohols Chemical class 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 92
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- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 239000007791 liquid phase Substances 0.000 claims abstract description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
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- 238000001816 cooling Methods 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 150000001299 aldehydes Chemical class 0.000 claims description 8
- 150000002576 ketones Chemical class 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 235000011089 carbon dioxide Nutrition 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- -1 copper aluminate Chemical class 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002594 sorbent Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000003345 natural gas Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 25
- 239000006227 byproduct Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 150000001875 compounds Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229960004424 carbon dioxide Drugs 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
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- 239000000571 coke Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
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- 239000011261 inert gas Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229940087654 iron carbonyl Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
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- 239000010970 precious metal Substances 0.000 description 1
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- 230000001131 transforming effect Effects 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/04—Gasification
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/10—Recycling of a stream within the process or apparatus to reuse elsewhere therein
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/42—Fischer-Tropsch steps
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- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
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Abstract
由包含氢气、一氧化碳、二氧化碳,和低级醇的醇合成气制备高级醇产物的方法。使用采用合成气作为汽提气的汽提器纯化含有低级和高级醇的液相从而从醇蒸气中汽提出低级醇。在制备高级醇的过程中,将用于汽提的合成气用作起始原料。
Description
本发明涉及高级醇的制备。尤其本发明是在一种或多种在一氧化碳和氢气至高级醇的转化中具有活性的催化剂存在下,通过转化与低级醇混合的含一氧化碳和氢气的合成气来制备这些醇的方法。
人们知道高级醇和其他含氧化合物(oxygenates)在从合成气催化合成甲醇中是作为副产物形成的。
人们也知道高级醇产物可由合成气直接制备。
美国专利申请No.2009/0018371公开了一种由合成气制备醇的方法。合成气在第一步骤中在第一催化剂的存在下部分转化为甲醇,在第二步骤中在第二催化剂的存在下,甲醇与第二量的合成气转化为包含C2-C4醇的产物。第二量的合成气可包括第一步骤中未反应的合成气。
合成醇要求合成气中一氧化碳高浓度。有用的合成气具有至少0.4且最高为3的H2/CO比例。用于高级醇合成的合成气是通过熟知的液态或气态烃蒸气重整方法或通过碳质材料,如煤、重油、石油焦和生物量气化制备的。
氢气与一氧化碳反应制备甲醇:
·合成气至甲醇
根据如下反应流程图,该甲醇与合成气反应,引发链增长得到高级醇:
·通过与合成气反应而链增长
等。
与传统甲醇合成气相比较,已发现向合成气中加入低级醇导致高级醇收率显著提高。很明显醇偶联在一起并形成高级醇:
·Aldol偶联
等。
如前文以及下面说明书和权利要求书中使用的,术语“低级醇”指存在于用来在高级醇合成中使用的醇合成气中的醇,术语“高级醇”指比醇合成气中的醇更高级的醇。
按照上述发现和观察,本发明的一般实施方式是一种制备高级醇产物的方法,其包括如下步骤:
(a)提供包括氢气、一氧化碳和低级醇的醇合成气;
(b)在一种或多种在醇合成气至高级醇的转化中具有活性的催化剂存在下,将醇合成气转化为包含高级醇和未转化的醇合成气的粗制醇产物料流;
(c)将取自步骤(b)的粗制醇产物料流冷却并分离为包含氢气、一氧化碳和二氧化碳的气相,和包含来自未转化醇合成气的低级醇和在醇合成气转化中形成的高级醇的液体产物;
(d)将步骤(c)得到的液体产物再循环至汽提处理并用新鲜的合成气汽提该液体产物;
(e)在步骤(d)中汽提液体产物后,从汽提处理中取出包含氢气、一氧化碳和已自液相汽提出的低级醇的合成气以提供步骤(a)的醇合成气;
(f)步骤(d)的液相汽提处理后,取出脱除低级醇的已汽提液相并将这样处理的液相进行分离处理;以及
(g)从步骤(f)的分离处理中回收高级醇产物。
在提供醇合成气的汽提处理中使用的新鲜合成气可通过烃蒸气重整或碳基进料气化产生。H2/CO比例可通过传统膜技术、甜和/或酸变换反应、二氧化碳再循环或本领域已知的其他方法调整。硫(如果存在)在硫保护床(sulphur guard)中或通过本领域已知的化学或物理洗涤脱除。
在合成气至高级醇的转化中有活性的催化剂本身为本领域已知,例如,来自US5096688、US4956392、US4675343和US4943551。为了在本发明中使用,优选的催化剂由铜、氧化锌和氧化铝组成,任选地用选自碱金属的一种或多种金属、碱土金属的碱性氧化物和镧系元素促进(promoted)。
醇合成可在带骤冷或夹层冷却的绝热操作反应器、气冷堆或优选在冷却管式沸水反应器中实施,冷却管式沸水反应器优选在反应器管道的管侧含沸水,并由此制备高压蒸气。用不同冷却剂冷却的其他反应器也适合在该发明中使用。
高级醇的合成优选在至少2MPa,典型地在2-15MPa之间的压力下和高于220℃,优选270-400℃的温度下进行。
如上文中提到的,醇如甲醇和乙醇参与高级醇的合成导致高级醇形成速率大幅度增加。
已经证明醇合成气中低级醇浓度升高导致高级醇产率增加。
因此,在该发明的实施方式中,进入汽提处理之前或在步骤(d)的汽提处理期间,在步骤(c)得到的包含低级和高级醇的液相与从分离步骤(f)的高级醇产物中分离出的低级醇料流混合。
在该发明特别有利的实施方式中,在步骤(c)中从液相分离出的含氢气和氧化碳的气相根据如下反应进行催化甲烷化:
CO+3H2=CH4+H2O;以及
CO2+4H2=CH4+2H2O
因此允许高级醇和替代天然气(SNG)的联合制备。
高级醇合成期间少量烷烃作为副产物形成。这些与气相中的氢气和氧化碳一起通入甲烷化反应并提高SNG的产率。
仍在本发明的一个实施方式中,通过将外部来源的低级醇料流加入到醇合成气中来促进高级醇的制备,如生物乙醇或粗甲醇产物等的料流。
在高级醇的合成中,少量醛、酮和酯以及其他含氧化合物(oxo-compounds)可作为副产物形成。这些副产物可与高级醇形成共沸混合物或具有与醇接近的沸点,导致产物纯化困难。
在本发明进一步的实施方式中,从醇合成步骤(b)中取出的粗制醇产物在氢化催化剂的存在下进行氢化步骤,其中包括含氧化合物的副产物氢化为它们对应的醇。因此,最终的产物蒸馏会大幅改善。
为了产物氢化的目的,该粗制醇产物在例如进料流出物换热器中冷却至100-220℃的温度,并引入包含氢化催化剂床的氢化反应器中。可用的氢化催化剂为包含贵金属包括铂和钯的催化剂,或醇合成中也使用的铜/锌氧化物/氧化铝催化剂。
醇合成气可进一步与外部来源的酮和/或醛混合。然后这些化合物在醇合成步骤中和在氢化步骤中部分氢化成它们相应的醇,这进一步增加了高级醇的产率。
在步骤(d)中液相汽提期间通过混合酮和/或醛料流,借助于再循环料流将该酮和/或醛有利地引入到合成气中。
当将氧化醇形成催化剂与具有高含量一氧化碳的合成气一起使用时,该催化剂操作时间减少。在一段接触反应时间(time on stream)后,该催化剂床将被蜡状物质阻塞,必须除去。
在提供相对高含量的一氧化碳的条件下,制备合成气期间出现这个问题。一氧化碳与合成气制备中使用的钢制设备反应并形成i.a.羰基铁化合物。当被转移到醇合成催化剂时,这些化合物催化Fischer-Trosch反应并在催化剂上形成蜡状物质。
通过从醇合成上游的新鲜合成气中除去羰基化合物,醇合成催化剂的操作时间可大大增加。
用于本发明方法的一种特别有用的羰基金属吸附剂包括改性的铜铝尖晶石,该改性是在与被羰基金属污染的合成气接触前,通过在氧化气氛下在升高的温度下煅烧,并接着在还原气氛,如合成气或用惰性气体稀释的合成气中还原。
优选地,该微粒状的吸附剂进一步包括氧化铜,氧化铜相较于在改性前的铜铝尖晶石中存在的量过量。
这些吸附剂从合成气中脱除羰基化合物至低ppb范围,优选低于1ppb。
本发明在下文说明书中参考附图更详细地描述,其中
图1为根据本发明具体实施方案的高级醇和SNG制备方法的简化流程图。
参考图1,醇合成气2通过来自汽提器13的顶部产物形成,其中包含低级醇和该方法制备的高级醇的粗制醇产物用新鲜合成气1作为汽提剂进行汽提,并作为顶部产品取出以提供醇合成气2,如下文更详细描述的那样。
将由此提供的醇合成气2引入高级醇合成反应器4。
来自合成反应器4的粗制醇产物5包含甲醇、乙醇、丙醇和高级醇,以及痕量的水和反应副产物,包括酮、醛、乙酸甲酯和甲酸甲酯。此外,它还包括气体化合物,包括氢气,一氧化碳和二氧化碳。
为除去或减少醛、酮和酯的量,将粗制醇产物5冷却(未显示)并通入氢化反应器6。这些和其他任选包含在粗制产品中的含氧化合物在氢化催化剂的存在下,用来自反应器4的未转化的合成气所包含的氢气氢化。
该氢化的粗制醇产物7被冷却(未显示)。冷却的产物在分离器8中分离为气相和液相,分别为9和17。
然后至少一部分气相9通过管线10至甲烷转化器11,用于制备从管线12取出的SNG。
气相9中的氢气含量可通过将来自例如合成气纯化步骤的在管线21中的富氢气体混合入气相9来提高。
从分离器8取出的液相17通过管线14至汽提器13。
汽提器13以这样的方式操作,以致不易挥发的高级醇作为底部产物15与未被汽提的残留量的低级醇共同离开汽提器进入醇合成气2。部分量的低级醇作为顶部产物与新鲜合成气1共同离开汽提器并形成醇合成气2。汽提器流出物料流15中的低级醇的量少于汽提器进料管线14中的低级醇的量。
用新鲜合成气汽提的液体料流14是在加热器(未显示)中预热的三股单独料流的混合物。这些料流中的第一股是汽提器液体流出物15的分流16。将液体流出物15的剩余部分通入蒸馏区域19进行分离处理。
第二股料流是来自分离器8的液相17,第三股为来自蒸馏区域19的顶部馏分18,其包含在蒸馏区域19中与高级醇分离的低级醇。不易挥发的高级醇与底部产物一起离开蒸馏区域。
如上文中提到的,少量烷烃副产物在高级醇合成期间形成。该烷烃副产物与少量二氧化碳一起溶于液体流出物17。为避免烷烃和二氧化碳的量在合成回路中增加,可使流出物17通入闪蒸槽(未显示),其中烷烃副产物和二氧化碳在液体流出物17通入汽提器13之前,作为气相分离。然后使该来自闪蒸槽的气相通过甲烷转化器11。
Claims (13)
1.制备高级醇产物的方法,其包括如下步骤:
(a)提供包括氢气、一氧化碳和低级醇的醇合成气;
(b)在一种或多种在醇合成气至高级醇的转化中具有活性的催化剂存在下,将醇合成气转化为包含高级醇和未转化的醇合成气的粗制醇产物料流;
(c)将取自步骤(b)的粗制醇产物料流冷却并分离为包含氢气、一氧化碳和二氧化碳的气相,和包含来自未转化醇合成气的低级醇和在醇合成气转化中形成的高级醇的液体产物;
(d)将从步骤(c)得到的液体产物再循环至汽提处理并用新鲜的合成气汽提该液体产物;
(e)在步骤(d)中汽提液体产物后,从汽提处理中取出包含氢气、一氧化碳和已自液相汽提出的低级醇的合成气以提供步骤(a)的醇合成气;
(f)步骤(d)的液相汽提处理后,取出脱除低级醇的已汽提液相并将这样处理的液相进行分离处理;以及
(g)从步骤(f)的分离处理中回收高级醇产物。
2.权利要求1的方法,其中步骤(b)中的一种或多种催化剂包含铜、氧化锌和氧化铝,并任选地用选自碱金属的一种或多种金属、碱土金属的碱性氧化物和镧系元素促进。
3.权利要求1或2所述的方法,其中包括进一步的步骤,即将包含低级醇的料流引入步骤(d)的汽提处理,所述低级醇在步骤(f)分离处理中从汽提的液相中分离。
4.权利要求1-3任一项所述的方法,其包括进一步的步骤,即冷却来自步骤(b)的粗制醇产物;并在引入步骤(c)之前,使该冷却的产物在氢化催化剂的存在下与氢化催化剂接触。
5.权利要求1-4中任一项所述的方法,其中通过使新鲜合成气与包含铜铝尖晶石的吸附剂接触来减少新鲜合成气中存在的羰基化合物的量,所述铜铝尖晶石在与合成气接触之前在200℃-500℃的温度下于还原气氛中通过还原改性。
6.权利要求5所述的方法,其中所述吸附剂包含相较于在铜铝尖晶石中包含的铜的量过量的铜。
7.权利要求1-6中任一项所述的方法,其中所述醇合成气的转化是在2-15MPa的压力和高于220℃的温度下进行的。
8.权利要求4所述的方法,其中所述氢化催化剂包含铜、氧化锌和氧化铝。
9.权利要求4所述的方法,其中所述氢化催化剂包含铂和/或钯。
10.前述权利要求中任一项所述的方法,其中将另外的外部低级醇料流引入步骤(b)上游的醇合成气中。
11.权利要求4所述的方法,其中将另外的含酮和/或醛的料流引入步骤(b)上游的醇合成气中。
12.权利要求11所述的方法,其中所述另外的酮和/或醛的料流在步骤(d)的汽提处理期间引入。
13.前述权利要求中任一所述的方法,其中至少一部分从步骤(c)的粗制醇产物中分离的气相通过将该至少一部分气相进行催化甲烷化来转化为替代天然气。
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