CN101594936B - 用于甘油脱水的催化剂的再生方法 - Google Patents
用于甘油脱水的催化剂的再生方法 Download PDFInfo
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- CN101594936B CN101594936B CN200780050632.7A CN200780050632A CN101594936B CN 101594936 B CN101594936 B CN 101594936B CN 200780050632 A CN200780050632 A CN 200780050632A CN 101594936 B CN101594936 B CN 101594936B
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Classifications
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Abstract
本发明涉及一种再生催化剂的方法,所述催化剂用于从甘油制备丙烯醛,所述催化剂包含钨的化合物,并具有酸的性能,并且包含至少一种促进剂。
Description
本发明涉及用于再生催化剂的方法,所述催化剂用于从甘油制备丙烯醛,并且所述催化剂包含钨化合物,具有酸性性能,并且包含至少一种促进剂。
背景技术
丙烯醛是重要的中间体,并且对于制备丙烯酸、D,L-甲硫氨酸和甲硫氨酸羟基类似物2-羟基-4-甲硫基丁酸(MHA)具有巨大的经济意义。甲硫氨酸是极其重要的氨基酸,其用作饲料中的添加物。现在,改善营养的饲料添加剂是动物营养中不可缺少的组分。它们用于更好地利用食物供应,刺激生长并且促进蛋白质形成。这些添加剂中最重要的之一是极其重要的氨基酸,即甲硫氨酸,特别是在家禽饲养中,甲硫氨酸作为饲料添加剂占据突出的位置。但是,在该领域中,甲硫氨酸的替代物,例如甲硫氨酸羟基类似物(简写成MHA)的重要性也不是微不足道的,这是因为与氨基酸的已知的生长刺激性能相比,它们具有类似的生长刺激性能。丙烯酸是用于制备聚合物的重要的起始材料,例如由于它们的吸水性,将丙烯酸用作高吸水性物质。
根据现有技术,通过在混合氧化物催化剂上非均相催化,来选择性氧化丙烯,进而合成丙烯醛。EP 417723描述了在300-380℃的温度和1.4-2.2bar的压力下,在复合混合多金属氧化剂催化剂上的合成。Ullmann’sEncyclopedia of Industrial Chemistry,第6版,1999,描述了包括综合加工(workup)在内的整个方法,其中,除去了许多副产品。一旦在催化剂上已经至少部分地将丙烯、空气和水的反应物混合物转化,首先进行骤冷以除去高沸点副产品,例如聚合物、丙烯酸和乙酸。在下游吸收剂中,冲洗丙烯醛。在脱附之后,对于通过在若干个阶段中蒸馏而获得的粗丙烯醛,通过将其纯化来回收吸收剂。
已知可以在酸性物质的存在下将甘油脱水形成各种产品。根据Organic Synthesis I,15-18(1964),在190-200℃处理粉末状硫酸氢钾、硫酸钾和甘油的混合物,提供了收率在33-48%之间的丙烯醛。但是,由于低的收率和高的盐负荷,该方法不适于工业规模。
在研究生物质热解油的典型物质的期间,也已经研究了在350-500℃在H-ZSM5沸石上催化处理甘油-参见Dao,Le H.等,ACS Symp.Ser.:376(热解油Biomass)328-341(1988)。仅以低收率形成烃。
此外,EP 0598229、US 5387720描述了在气相中和在液相中将甘油酸-催化转化成丙烯醛。在这种情况下,决定是否适宜作为催化剂的因素仅有酸强度(Hammett酸函数)。DE 4238492涉及通过将甘油脱水,从而以高收率合成1,2-和1,3-丙二醇。
WO 2006/087083公开了在酸性催化剂上从甘油制备丙烯醛的方法,其中,将氧添加到反应混合物中。
在WO 2006/087084中描述了类似的方法,其中所用的催化剂其Hammett酸度H0在-9至-18的范围内。
在化学技术中采用的催化剂近乎毫无例外地会发生钝化,从而不得不以周期性的间隔交换催化剂,以便保持经济的时空产率。催化剂的寿命依反应体系的不同而非常不同,并且可能是几小时至几年。催化剂的周期性再生至少部分地抵消钝化,并且此外还显著地增加催化剂的活性。当在催化剂上形成覆盖活性部位的含碳沉积物时,在工业上经常将其用于合成中。这些沉积物依反应体系的不同而不同。作为改善可再生性的本发明催化剂的选择以及促进剂的添加,可以在甘油的脱水中改善时空产率。
发明内容
本发明的一个目的是提供一种适用于甘油脱水的催化剂的再生方法,该催化剂具有相对较低的碳化倾向并且易于再生。
已经发现,包含钨的化合物、一种或多种促进剂,并且Hammett酸度Ho<+2固态催化剂解决了该问题,其中所述促进剂选自包含金、银、铜、钒、铂、铑、钯、钌、钐、铈、钪、钇、镧、锌、镁、铁、钴或镍中的元素的化合物、以及任选存在的元素锂、钠、钾或铯的化合物、和/或蒙脱石或酸性沸石,所述促进剂优选由金、银、铜、钒、铂、钯、铑、钌、钐、铈、钇、钪、镧、锌、镁、铁、钴或镍或它们的混合物组成。
元素锂、钠、钾或铯的化合物、蒙脱石或酸性沸石作为促进剂存在于催化剂中,任选存在的含量为0.1-30重量%,优选5-25重量%。
优选Hammett酸度H0为<+2至-20的催化剂。
由于甘油是反应性分子,它倾向于在高温下通过两个或多个甘油分子彼此反应来形成相对高沸点的化合物,通过在表面上沉积含碳分子,将催化剂碳化。这导致活性减小。
为了实现高的时空产率,不仅催化剂的Hammett酸强度很重要,而且可再生性和碳化倾向也很重要。
本发明所用的催化剂包含至少一种加速催化剂再生的促进剂。寿命和时空产率同样显著地增加,这是因为,在这些催化剂的情况下,至少在最大程度上消除了特别是因碳化导致的钝化,并且活性显著增加。从而,甘油的转化和丙烯醛的收率可以根据时间保持在高水平。特别是对于工业上进行合成,这具有极大的重要性,这是因为催化剂的交换以及相关的工厂停车会引起高成本。
除了-酸性基团之外,羟基基团或Lewis-酸性部位也可以影响活性和选择性。同样地,除了促进剂之外,向包含钨的化合物的催化剂中添加一种或多种选自硅、磷、铌、锌、锡、镁、铝、钼或钒或活性炭中的元素的化合物,可以改变催化剂的表面或减小活性部位的浓度,从而进一步改善收率。这特别是减少了高沸点化合物(boiler)或焦炭前体的形成,所述高沸点化合物或焦炭前体是从两种或多种相邻的被吸附的甘油分子或中间体形成的,并且以固定的方式被吸附。
适合的固态催化剂也特别是从US 5,387,720(EP 0 598 229 A1)中已知的类型,这时,它们包含钨的化合物和另外的一种或多种所提及的促进剂。这些催化剂是基本不溶于反应介质的固体物质,它们具有单相或多相结构,并且其Ho小于+2,优选小于-3。Ho相应于Hammett酸度函数,并且可以通过采用指示剂的所谓的胺滴定或通过气态碱的吸附来测定,参见Studiesin surface science and catalysis,Vol.51,1989:“New solid acids and bases,theircatalytic properties”,K.Tanabe等人,第2章,特别是第5-9页。前述文献的第1章(第1-3页)提及了许多固体酸,由此,如果合适的话,本领域技术人员在测定Ho值之后,可以选择用于本发明改进的合适的催化剂。本发明的脱水催化剂的适合的基本物质优选(i)天然的合成的硅酸盐物质(silicatic substance),特别是丝光沸石、酸性沸石和活性炭;(ii)载体材料,例如氧化或硅酸盐物质,例如Al2O3、SiO2、ZrO2、TiO2;(iii)氧化物和混合氧化物,例如γ-Al2O3和ZnO-Al2O3、SiO2-Al2O3、ZrO2-SiO2、ZrO2-HfO2混合氧化物或杂多酸。
提供活性钨部位的合适的化合物例如可以是钨酸铵、偏钨酸铵、钨酸、钨硅酸、钨磷酸或含有钨作为组分的杂多酸。然后,将这些化合物或它们的混合物直接用作催化剂或用作催化剂前体。在添加其它元素的情况下,优选在溶液或在熔化物中作为粉末在先混合。在本发明的一个实施方案中,将催化活性化合物结合在载体上。
所用的载体材料例如可以是氧化铝、二氧化钛、二氧化硅、二氧化锆、活性炭或它们的混合物。载体主要用来增加比表面积或用来固定活性部位。
通过本领域技术人员已知的方法来制备本发明所用的催化剂。当将活性成分应用于载体时,优选通过浸渍载体来进行所述应用,例如通过喷射始润(incipient-wetness)方法。也可以通过从溶液中沉淀或萃取来获得活性成分。随后,然后可以将催化剂成型,如果合适的话,通过压制、挤出、涂布或附聚来添加载体、粘合促进剂或成孔剂。典型地,催化剂的粒径在0.04mm-20mm之间,优选在0.1-10mm之间,特别是在0.5-7mm之间。也可以涂覆的形式应用活性化合物。当不采用载体时,优选通过挤出、压制成片或通过附聚集结来制备催化剂。
对于在气相中的脱水,特别优选Ho在-3至-8.2之间的催化剂。包含钨和促进剂的合适的催化剂体系例如是,SiO2/H2WO4、Pd/H2WO4、Pt/H2WO4、Pd/WOx/ZrO2、Cu/WOx/ZrO2、WOx/SiO2/ZrO2。
在固态催化剂的存在下,进行通过甘油脱水来制备丙烯醛的方法,所述固态催化剂包含钨的化合物,所述催化剂的Hammett酸度Ho为<+2至优选-20,并且所述催化剂包含一种或多种促进剂,所述促进剂选自包含金、银、铜、钒、铂、钯、铑、钌、钐、铈、钇、钪、镧、锌、镁、铁、钴或镍中的元素的化合物或它们的混合物,所述促进剂优选由金、银、铜、钒、铂、钯、铑、钌、钐、铈、钇、钪、镧、锌、镁、铁、钴或镍或它们的混合物组成。此外,元素锂、钠、钾或铯的化合物、和/或蒙脱石或酸性沸石是任选存在的。
元素锂、钠、钾或铯的化合物、蒙脱石或酸性沸石作为促进剂存在于在催化剂中,任选其存在量为0.1-30重量%,优选5-25重量%.
优选在不存在氧的情况下进行脱水。在一个具体实施方案中,也在氢气的存在下进行所述脱水,基于反应混合物的总量,氢气的量为0.1-10体积%,特别是0.5-5体积%。在上述催化剂的存在下进行脱水。
优选通过添加在所选的反应条件下惰性的合适的气态化合物,来降低甘油在反应混合物中的浓度。
结果,将得到低聚物、聚合物和其它高沸点化合物的副反应最小化。采用本领域技术人员已知的溶剂和稀释剂,例如水、氮气、空气、二氧化碳、甲烷和/或氢气、醇例如甲醇和乙醇、丙酮、甲苯或甲基异丁基酮。优选在冷凝之后,可以简单方式通过相分离来将稀释介质与丙烯醛分离。
在反应混合物中,甘油浓度在1-100重量%之间,优选在1-70重量%之间,特别是在5-40重量%之间。
该方法的一个优点在于这样的事实,即,也可用含量为5-40重量%的甘油溶液。从而,可以将没有预先浓缩或纯化的所谓的粗甘油直接用于合成丙烯醛。
在150-450℃之间的温度下,优选在180-350℃之间,更优选在220-320℃之间的温度下进行反应。典型地,压力在0.1-200bar之间,优选在0.5-50bar之间,更优选在0.9-10bar之间。
可以在液相或在气相中进行所述方法。在两个实施方案中,原则上都可以采用同样的酸性固态催化剂,但是已经发现,特别的催化剂优选适合于在气相中脱水,并且其它的优选适合于在液相中脱水。
在气相中的反应是特别优选的,这是因为甘油转化近乎完全(>95%),并且,可以将离开催化剂的气态反应混合物冷凝或直接吸收,以获得丙烯醛水溶液,所述水溶液还包含已经形成的副产品;在许多情况下,可以直接将该冷凝物进一步加工。可以在许多阶段中进行反应混合物的部分冷凝和/或吸收。如果希望的话,通过分凝、吸收、脱附和随后的蒸馏,可以从反应混合物获得丙烯醛,如果合适的话,还可以同时获得一部分水。
将一部分水循环,在此期间,将这部分水蒸发和浓缩,同时利用热。
也可以将惰性气体或稀释剂循环。
在液相中反应的情况下,进行脱氢直至甘油的转化率仅为不超过约15-25%时是合适的,这是因为当转化率增加时选择性降低。在已经实现所述转化之后,以已知方式,典型地通过蒸馏或通过N2气提,仅从反应混合物中或从反应混合物与一部分水中除去形成的丙烯醛。可以通过冷凝或用水洗涤来分离丙烯醛。将含有甘油同时不含丙烯醛的反应混合物再循环到脱水阶段中。与在气相中脱水相比,在液相中脱水的一个优点在于较低的能量需求,这是因为必须将从反应混合物中除去的仅丙烯醛和与丙烯醛一起蒸馏掉的一部分水蒸发。
在气相中的脱水优选在240-320℃之间的温度范围内进行,在液相中的脱水优选在250-300℃之间进行。在液相脱水的情况下,使装置处于至少足以保持液相的压力下。
在固定床反应器、流化床反应器、具有循环流化床的反应器、移动床反应器或具有再生器提升管(regenerator-riser)(-下降管,downer)设计的反应器中进行脱水。可以连续或分批进行。
此外,通过反应性蒸馏将反应与反应物综合加工(workup)或产物综合加工组合起来是可能的并且是可取的,这是因为甘油与丙烯醛之间的沸点差非常大。在这种情况下,将催化剂置于底部和/或置于塔部分。引入的催化剂例如可以床、悬浮体或涂层的形式存在。反应性蒸馏的另一个优点在于这样的事实,将高沸点杂质与其它作为副产品形成的高沸点化合物从粗甘油中在塔底部排出。然后通过塔顶除去丙烯醛和低沸点物质。
也可以已知方式,通过气提、蒸馏或萃取从反应混合物中单独地或与一部分溶液或稀释介质一起除去形成的丙烯醛。然后,可以将未转化的甘油再循环到反应阶段中。
本发明所用催化剂也因其良好可再生性而值得注意。
本发明提供一种使固态催化剂再生的方法,所述固态催化剂包含钨的化合物,所述催化剂的Hammett酸度Ho为<+2至优选-20,并且所述催化剂包含一种或多种促进剂,所述促进剂选自包含优选选自由金、银、铜、钒、铂、钯、铑、钌、钐、铈、钇、钪、镧、锌、镁、铁、钴或镍组成的元素组中元素的化合物或它们的混合物、任选添加的元素锂、钠、钾或铯的化合物、和/或蒙脱石或酸性沸石,所述促进剂优选由金、银、铜、钒、铂、钯、铑、钌、钐、铈、钇、钪、镧、锌、镁、铁、钴或镍或它们的混合物组成,在用于将甘油脱水生成丙烯醛的过程中之后,所述催化剂的活性和/或选择性比将其用于该脱水方法之前的活性和/或选择性低,其中,将所述催化剂暴露于用于所述再生的氧化或还原气氛中,而不需要甘油脱水的反应物的存在。
根据它们的标准电势,在还原条件下再生催化剂之后,各个元素也可以金属的形式存在于催化剂之上。
包含钨的化合物选自钨酸铵、钨磷酸、钨酸、钨硅酸、钨氧化物或含有钨作为组分的杂磷酸。特别适合的例子是Pd/H2WO4、Pt/H2WO4、PdWOx/ZrO2、Ce/WOx/ZrO2。
催化剂优选包含天然的或合成的硅酸盐化合物或氧化化合物作为载体。
也适合的是包含用一元、二元或多元无机酸或无机酸的盐改性过的载体材料的催化剂。
也优选包含氧化铝、二氧化钛、二氧化硅、二氧化锆、活性炭或它们的混合物作为载体材料的催化剂。
可以在氧化条件或在氢化条件下进行再生。在这两种情况下,完全或部分地除去在反应过程中通过烃的沉积在催化剂表面形成的焦炭。适合的作为催化剂一部分的促进剂,在通过氧化再生的情况下,通常为加速烃转化成碳氧化物的成分,例如是金、银、铜、钒或铂,任选为金属的形式;当在氢化条件下进行再生时,将具有强烈氢化作用的促进剂添加到酸性催化剂中,例如钴、镍、钯、铂或铑。
再生与甘油转化在时间或在空间上分开进行。在时间上分开的情况下,停止将甘油供给到反应器中,然后,在再次供给反应物混合物之前进行再生。然后,根据所期望的,多次周期性地重复该操作。对于该再生方法的进行,适合的安排特别是循环操作2个或更多个固定床反应器,从而能够获得连续的产物流。在这种情况下,将反应器中的一个再生,同时采用反应器中的至少一个来制备丙烯醛。可以根据期望来选择反应与再生的时间间隔。优选地,在0.5-100h,特别是1-10h的时间间隔内再生催化剂之前,在2-3000h的时间间隔内,特别是在4-400h的时间间隔之内连续制备丙烯醛。
当在分隔的位置进行再生时,优选在2个反应器间连续移动催化剂。在一个反应器中,将甘油转化成丙烯醛连续发生。在另一个反应器中,将催化剂连续再生。适合的反应器设计是移动床反应器或再生器提升管(-下降管)设计。因为相对较低的催化剂通过量和较少的催化剂磨损,移动床是值得注意的并且在此优选。
在再生与反应之间,在每种情况下,进行冲洗步骤都是可取的,优选采用氮气进行冲洗。在再生的情况下,采用100-800℃,优选200-700℃,特别是300-550℃的较高的温度。这些不需要相应于甘油转化过程中的反应器温度。在这种情况下,需要相应的加热和冷却步骤。对于催化剂的再生,优选采用比在反应中更高的温度。再生中的压力优选在0-50bar之间,特别是在0-3bar之间。
为了使催化剂再生,采用至少一种添加剂。这优选是气态的。当在氧化条件下进行再生时,所述添加剂是气态氧化剂。优选采用空气或氧。也可以采用二氧化碳或其它氧化剂。此外,可以添加水或水蒸汽。当通过氢化进行再生时,所述添加剂是气态还原剂。在这种情况下,优选采用氢气。为了避免由于除去焦炭时放热而在催化剂区域中温度过高,优选以稀释过的形式使用还原气体,为此,例如,采用氮气或蒸汽。在再生催化剂的过程中,优选逐步增加添加剂的浓度。可以通过采用固体惰性材料或通过将催化剂排列在在不同区域中,来稀释催化剂。
也可以采用用于再生的氧化剂和还原剂的混合物。在这种情况下,但是,与另一种再生剂相比,所用的再生剂之一优选过量存在。
如所观察到的,通过再生使用钨和促进剂,催化剂的期望的催化性能和/或酸功能不会消失,而例如,在常规的酸,例如磷酸或盐酸作为催化剂的情况下,这导致催化剂钝化。
具体实施方式
实施例
对比例1:
采用根据专利说明书DE 4238493的催化剂:将直径约4mm的100g氧化硅载体与25g的20重量%磷酸混合1h。然后,在旋转蒸发器上,在约70℃将过量的水除去。将18ml的该催化剂引入到直径15mm的固定床反应器中。然后,将反应加热到250℃的温度。通过泵,通过加热到260℃的蒸发器将12.5g/h的20重量%甘油水溶液通入到反应器中。通过气相色谱法,在反应器出口分析物流。直到操作时间为约15h,可以观察到甘油完全转化。选择性进而收率为79%。在约15h之后,转化进而收率急剧下降,从而,在23h之后,仅有20%的转化率。在350℃的温度下,仅通过4l(STP)/h的氢气流,流过催化剂5h之后,不能检测到收率(再生)的改进。在350℃的温度下,仅通过4l(STP)/h空气流,流过催化剂5h之后,甚至检测到收率的进一步降低。
对比例2:
重复对比例1,除了将压制成片的钼酸用作催化剂外。在250℃的反应器温度下,在开始的5h中获得9%的收率。省却再生。
实施例1:
重复对比例1,除了将压制成片的钨酸用作催化剂外。在260℃的反应器温度下,在开始的5h内获得完全转化和79%的收率。在接下来的操作时间(以小时计)中,转化显著降低,并且收率相应地也显著地降低。在进一步的过程中,检测到每10h收率下降约5%。在350℃的温度下,仅通过4l(STP)/h的氢气流,流过催化剂10h之后,催化剂活性得到显著改进。起始时,甘油再次完全转化。在进一步的过程中,转化和收率减少,如同再生之前一样。在300h内,将甘油脱水和催化剂再生的循环操作重复3次。在已经将未再生的催化剂卸载之后,所述催化剂的颜色是黑色的。催化剂的碳含量为22重量%,这说明碳化非常严重。
实施例2:
重复对比例1,除了将压制成片的钨酸用作催化剂外。另外用1重量%的Pd浸渍该催化剂。为此,通过始润来使用乙酸铅。在260℃的反应器温度下,在开始的5h内获得完全转化和77%的收率。在接下来的操作时间(以小时计)中,转化显著降低,并且收率相应地也显著地降低。在350℃的温度下,仅通过4l(STP)/h的氢气流,流过催化剂10h之后,催化剂活性得到显著改进。然后,起始时,甘油再次完全转化。与实施例1相比,在再生之后,脱水反应中转化率的下降显著减弱,并且高转化水平保持得更久。
实施例3:
重复对比例1,除了将15重量%的蒙脱石和85重量%的压制成片的WO3/ZrO2(在ZrO2上的11重量%WO3)的粉末状混合物用作催化剂外。在260℃的反应器温度下,在开始的5h内获得完全转化和79%的收率。在接下来的操作时间(以小时计)中,转化降低,并且收率相应地也降低。在300℃的温度下,仅通过4l(STP)/h的空气流,流过催化剂5h之后,催化剂活性得到显著改进。在再生的第一小时期间,用氮气将空气1∶1稀释,以限制由于焦炭燃烧引起的放热。在再生之后,起始时甘油再次完全转化。在已经经过了脱水和再生的6个循环之后,将再生温度增加到390℃。在随后的脱水中,这导致显著增强的转化率分布,其中,在约20h之后,甘油转化率仍然大于90%。
Claims (14)
1.一种使固态催化剂再生的方法,所述固态催化剂包含钨的化合物,所述催化剂的Hammett酸度Ho<+2,并且所述催化剂包含钯作为促进剂,任选地包含元素锂、钠、钾或铯的化合物、和/或蒙脱石或酸性沸石,在用于将甘油脱水生成丙烯醛的过程中之后,所述催化剂的活性和/或选择性比上述使用之前的活性和/或选择性低,其中,将所述催化剂暴露于用于再生的还原气氛。
2.根据权利要求1所述的方法,其中,将Hammett酸度Ho为<+2至-20的催化剂再生。
3.根据权利要求1所述的方法,其中,将如下催化剂再生,在所述催化剂中,所述包含钨的化合物选自钨酸铵、钨磷酸、钨酸、钨硅酸或含有钨作为组分的杂多酸。
4.根据权利要求2所述的方法,其中,将如下催化剂再生,在所述催化剂中,所述包含钨的化合物选自钨酸铵、钨磷酸、钨酸、钨硅酸或含有钨作为组分的杂多酸。
5.根据权利要求1-4中任一项所述的方法,其中,将如下催化剂再生,所述催化剂包含天然的或合成的硅酸盐化合物或氧化物。
6.根据权利要求1-4中任一项所述的方法,其中,将如下催化剂再生,所述催化剂包含载体材料,所述载体材料用一元、二元或多元无机酸或无机酸的盐进行了改性。
7.根据权利要求5所述的方法,其中,将如下催化剂再生,所述催化剂包含氧化铝、二氧化钛、二氧化硅、二氧化锆、活性炭或它们的混合物作为载体材料。
8.根据权利要求1-4和7中任一项所述的方法,其中,在还原条件下将催化剂再生,所述催化剂还包含除了钯之外的选自以化合物的形式或者以金属的形式的钴、镍、铑或铂的促进剂。
9.根据权利要求1-4和7中任一项所述的方法,其中,甘油脱水之间的催化剂的再生时间小于24h。
10.根据权利要求1-4和7中任一项所述的方法,其中,在所述催化剂的存在下,甘油脱水的反应时间大于10h。
11.根据权利要求1-4和7中任一项所述的方法,其中,所述催化剂的再生温度在260-550℃之间。
12.根据权利要求1-4和7中任一项所述的方法,其中,所用的再生剂是氢气。
13.根据权利要求1-4和7中任一项所述的方法,其中,在固定床反应器、流化床反应器、移动床反应器或具有再生器提升管设计或具有再生器下降管设计的反应器中进行所述再生。
14.根据权利要求13所述的方法,其中,所述流化床反应器具有循环流化床。
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WO2013017904A1 (en) * | 2011-07-29 | 2013-02-07 | Arkema France | Improved process of dehydration reactions |
FR2989684B1 (fr) | 2012-04-18 | 2014-10-31 | Arkema France | Procede de fabrication d'acroleine et/ou d'acide acrylique a partir de glycerol |
FR2997398B1 (fr) * | 2012-10-30 | 2014-11-21 | Adisseo France Sas | Procede de preparation de l’acroleine a partir de glycerol |
SG11201509776VA (en) | 2013-06-03 | 2015-12-30 | Evonik Degussa Gmbh | Method for producing acrolein |
KR101774543B1 (ko) * | 2014-12-19 | 2017-09-04 | 주식회사 엘지화학 | 글리세린 탈수 반응용 촉매, 이의 제조 방법 및 상기 촉매를 이용한 아크롤레인의 제조 방법 |
KR101805086B1 (ko) * | 2015-03-02 | 2017-12-05 | 주식회사 엘지화학 | 글리세린 탈수 반응용 촉매의 제조 방법, 이를 이용하여 제조된 글리세린 탈수 반응용 촉매 및 아크롤레인의 제조 방법 |
US20160368861A1 (en) | 2015-06-19 | 2016-12-22 | Southern Research Institute | Compositions and methods related to the production of acrylonitrile |
CN105032419B (zh) * | 2015-07-18 | 2017-12-22 | 黑龙江中医药大学 | 一种双金属修饰的多酸化合物及其制备方法和应用 |
KR102052708B1 (ko) | 2015-12-22 | 2019-12-09 | 주식회사 엘지화학 | 글리세린 탈수 반응용 촉매, 이의 제조 방법 및 상기 촉매를 이용한 아크롤레인의 제조 방법 |
CN105749939B (zh) * | 2016-03-09 | 2018-03-30 | 浙江工业大学之江学院 | 一种磷酸改性蒙脱石负载钨氧化物催化剂、制备方法和应用 |
CN106008188B (zh) * | 2016-05-30 | 2018-05-29 | 浙江工业大学 | 一种甘油催化脱水制备丙烯醛的新方法 |
US9708249B1 (en) | 2016-08-24 | 2017-07-18 | Southern Research Institute | Compositions and methods related to the production of acrylonitrile |
CN109174075A (zh) * | 2018-09-04 | 2019-01-11 | 中国科学院上海硅酸盐研究所 | 一种用于光催化降解VOCs的稀土元素改性二氧化钛纳米光催化材料及其制备方法 |
CN112778088B (zh) * | 2021-01-14 | 2022-07-19 | 浙江工业大学 | 一种甘油同步制备丙烯酸和1,2-丙二醇的方法 |
CN114011457B (zh) * | 2021-12-07 | 2023-09-19 | 万华化学集团股份有限公司 | 一种对乙氧基苯酚的制备方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1090568A (zh) * | 1992-11-14 | 1994-08-10 | 底古萨股份公司 | 制备1,2-丙二醇和1,3-丙二醇的方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU52208A1 (ru) * | 1936-04-22 | 1936-11-30 | Ю.Н. Вольнов | Способ получени акролеина из глицерина |
SU701988A1 (ru) * | 1977-04-15 | 1979-12-05 | Предприятие П/Я Г-4647 | Способ получени акролеина |
US4837397A (en) * | 1987-12-11 | 1989-06-06 | Mobil Oil Corporation | Nobile metal containing catalysts of improved stability |
DE3930534A1 (de) | 1989-09-13 | 1991-03-21 | Degussa | Verfahren zur herstellung von acrolein durch katalytische gasphasenoxidation von propen |
DE4238493C1 (de) | 1992-11-14 | 1994-04-21 | Degussa | Verfahren zur Herstellung von Acrolein und dessen Verwendung |
US5608133A (en) * | 1995-10-23 | 1997-03-04 | Mobil Oil Corporation | Catalytic oligomerization |
FR2781393B1 (fr) * | 1998-07-22 | 2000-08-25 | Rhone Poulenc Fibres | Procede de regeneration d'un catalyseur d'hydrolyse cyclisante d'un aminonitrile en lactame et utilisation du catalyseur regenere pour la fabrication de lactames |
FR2841797B1 (fr) * | 2002-07-03 | 2005-08-05 | Centre Nat Rech Scient | Catalyseurs a base de tungstene |
FR2882052B1 (fr) | 2005-02-15 | 2007-03-23 | Arkema Sa | Procede de deshydratation du glycerol en acroleine |
FR2882053B1 (fr) | 2005-02-15 | 2007-03-23 | Arkema Sa | Procede de deshydratation du glycerol en acrolene |
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CN1090568A (zh) * | 1992-11-14 | 1994-08-10 | 底古萨股份公司 | 制备1,2-丙二醇和1,3-丙二醇的方法 |
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BRPI0721357B1 (pt) | 2017-04-04 |
BRPI0721357A2 (pt) | 2014-02-25 |
US20080214384A1 (en) | 2008-09-04 |
ES2611939T3 (es) | 2017-05-11 |
CN101594936A (zh) | 2009-12-02 |
DE102007004350A1 (de) | 2008-07-31 |
US7846861B2 (en) | 2010-12-07 |
EP2114564A1 (de) | 2009-11-11 |
MY145828A (en) | 2012-04-30 |
RU2484895C2 (ru) | 2013-06-20 |
RU2009132405A (ru) | 2011-04-10 |
WO2008092534A1 (de) | 2008-08-07 |
MX2009007863A (es) | 2009-07-31 |
JP5312347B2 (ja) | 2013-10-09 |
JP2010516462A (ja) | 2010-05-20 |
EP2114564B1 (de) | 2016-11-02 |
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