CN1678389A - 氧化法 - Google Patents
氧化法 Download PDFInfo
- Publication number
- CN1678389A CN1678389A CNA038205785A CN03820578A CN1678389A CN 1678389 A CN1678389 A CN 1678389A CN A038205785 A CNA038205785 A CN A038205785A CN 03820578 A CN03820578 A CN 03820578A CN 1678389 A CN1678389 A CN 1678389A
- Authority
- CN
- China
- Prior art keywords
- reaction
- described method
- oxidant
- oxidation
- initiation material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 47
- 230000003647 oxidation Effects 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 230000001590 oxidative effect Effects 0.000 claims abstract description 32
- 239000007800 oxidant agent Substances 0.000 claims abstract description 28
- 238000009835 boiling Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 33
- 230000000977 initiatory effect Effects 0.000 claims description 30
- 239000000376 reactant Substances 0.000 claims description 28
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 25
- 229930195733 hydrocarbon Natural products 0.000 claims description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 229930194542 Keto Natural products 0.000 claims description 4
- 125000000468 ketone group Chemical group 0.000 claims description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- WIRUZQNBHNAMAB-UHFFFAOYSA-N benzene;cyclohexane Chemical compound C1CCCCC1.C1=CC=CC=C1 WIRUZQNBHNAMAB-UHFFFAOYSA-N 0.000 claims 1
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 claims 1
- 238000010992 reflux Methods 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 24
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- 239000004215 Carbon black (E152) Substances 0.000 description 17
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
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- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
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- 229910052760 oxygen Inorganic materials 0.000 description 4
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 3
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
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- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
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- 239000001294 propane Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明涉及一种用氧化剂氧化反应物以获得产物的方法。该方法的特征在于:在反应装置(1)中进行氧化反应,所述反应装置(1)包括位于下端的底部区域,位于上端的顶部区域和位于底部区域和顶部区域之间的反应区(1);在反应区中将反应混合物保持在沸点;以及将氧化剂以至少两股子料流(5)引入反应区中。
Description
本发明涉及一种用氧化剂氧化起始原料以获得产物的方法,其包括:
在反应装置中进行氧化反应,所述反应装置具有位于下端的底部区域,位于上端的顶部区域和位于顶部区域和底部区域之间的反应区;
在反应区中将反应混合物保持为沸腾状态;以及
将氧化剂以至少两股子料流引入反应区中。
已经知道许多种用含分子氧的气体氧化起始原料,特别是有机起始原料以获得产物的方法。
例如,可以将饱和化合物转化为不饱和化合物,例如将甲基环己烷转化为甲苯或者将丙烷转化成丙烯;可将醇转化为醛或酮,例如将异丙醇转化为丙酮,将仲丁醇转化成甲基乙基酮或将甲醇转化成甲醛;可将烃转化为氢过氧化物,例如将枯烯转化为氢过氧化枯烯、将1,2,3,4-四氢化萘转化为氢过氧化1,2,3,4-四氢化萘或将环己烷转化为氢过氧化环己烷;可将烯烃转化为环氧化合物,例如将乙烯转化为氧化乙烯;或者将烃转化为醇、醛、酮或羧酸,例如将环己烷转化为环己醇或环己酮,将甲苯转化为苯甲醛或苯甲酸,将邻-、间-、对-二甲苯转化为相应的芳族二元羧酸或其酸酐,将丁烷转化为马来酸酐或将丙烯转化为丙烯醛或丙烯酸。
这类氧化反应的问题之一是具有价值的所需产物本身可能发生氧化,获得不需要的副产物或最终转化为二氧化碳和水。这会不利地导致氧化反应的选择性降低。
一种工业上重要的氧化反应描述在Weissermel/Arpe,IndustrielleOrganische Chemie(工业化学百科全书),第四版,VCH,Weinheim,1994,第260页及往下各页中,其为将环己烷氧化为含有环己醇和环己酮的混合物的反应,该反应在125至165℃的温度和8至15巴(绝对)的压力下在作为催化剂的锰盐或钴盐存在下使用空气在液相中进行。
在这种氧化反应中,为了达到工业上适用的选择性,环己烷的转化率受到限制。根据Arpentier等人,The Technology of Catalytic Oxidations(催化氧化技术),Editions Technip 2001,第226页及往下各页,当环己烷的转化率为1至2%时,选择性大约为90%,而当转化率甚至为4至5%时,选择性降到77至85%。
未转化的环己烷必须在下游蒸馏塔中蒸出,并再循环入氧化段中。
环己醇和环己酮是制备己内酰胺和己二酸的起始原料,而己内酰胺和己二酸又极大程度上用作工业上制备重要的聚酰胺的单体。
DE 19811517描述了在对臭氧呈惰性的反应器中通过经由塔顶计量加入臭氧而使用臭氧将环己烷转化为环己酮的非催化选择性氧化反应,同时连续取出塔底形成的环己酮产物。
这种方法的缺点是氧化剂与起始原料接触不充分,并且氧化剂的应用性差:在工业上相关的压力下,臭氧是气体,因此会尚未与待氧化烃充分接触而再次离开反应器。
此外,所述方法倾向于在低于或等于待氧化环己烷的沸点的温度下进行。然而,由于反应产物的沸点比起始原料的沸点高大约75℃,反应混合物的沸点因而也高于环己烷的沸点,因此这种方法是没有蒸馏的纯液相反应。因此,这种方法也具有上述提到的有关反应混合物的分离和环己烷的再循环的缺点。
本发明的目的是提供一种使用氧化剂将起始原料,特别是有机起始原料进行氧化反应以获得产物的方法,该方法技术上简单并且经济,同时又避免了上述缺点。
我们已经发现,这个目的通过本申请开头定义的方法得以实现。
根据本发明,本发明方法适合氧化起始原料。
有用的起始原料是无机化合物,但优选有机化合物。
有用的有机化合物可以是不饱和烃,但优选饱和烃。在这些烃中,一个或多个碳原子可以被诸如氧原子、氮原子、硫原子或磷原子的杂原子替代,其中这些杂原子的任何自由价键被氢或取代基,特别是下面所述的烃取代基饱和;优选碳原子不被上述杂原子替代。对于本发明而言,有和没有这些杂原子的烃均总称为烃。
有用的不饱和烃包括具有一个或多个叁键,一个或多个烯属双键或芳族体系的那些烃,或者具有上述特征组合的那些烃,例如乙烯、丙烯、1-丁烯、2-丁烯、1,3-丁二烯、苯、甲苯、邻二甲苯、间二甲苯、对二甲苯、芴、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶和1,2,3,4-四氢化萘。有用的不饱和烃可以是线性或环状的。
有用的饱和烃可以是线性烷烃或优选环烷烃,特别是具有2至12个碳原子的那些烃。
有利的线性烷烃是乙烷、丙烷、正丁烷、异丁烷、正戊烷、正己烷、正庚烷、正辛烷、正壬烷和正癸烷。
有用的环烷烃可为环己烷和十氢化萘。
所述烃可以是取代或未取代的,例如被脂族基团取代,优选被下述基团取代:C1-C8烷基,例如甲基、乙基、异丙基、正丙基、正丁基、异丁基、仲丁基、正戊基、正己基、正庚基、正辛基、2-乙基己基,OH,=O,C1-C8烷氧基,COOH,C2-C6烷酯基,C1-C10酰氧基或C1-C8烷基氨基,磺酸或其盐,例如碱金属盐或碱土金属盐,或酯,氰基,或卤素,例如氟、氯或溴。
在有利的实施方案中,本发明方法可以用于将烃或醛氧化为例如可用于烯烃的非直接环氧化的氢过氧化物,例如将乙醛氧化为过乙酸、将异丁烷氧化为过氧化异丁基、将异戊烷氧化为过氧化异戊基、将乙基苯氧化为过氧化苯乙基、将枯烯氧化为氢过氧化枯烯或将1,2,3,4-四氢化萘氧化为氢过氧化1,2,3,4-四氢化萘。
在进一步有利的实施方案中,本发明方法可以用于将烃或醛氧化为酸或其酸酐或其酯,例如将对二甲苯氧化为对苯二甲酸、将间二甲苯氧化为间苯二甲酸、将邻二甲苯氧化为邻苯二甲酸或邻苯二甲酸酐、将正丁烷氧化为乙酸、将甲苯氧化为苯甲醛或苯甲酸、将烷属烃氧化为酸、将乙醛氧化为乙酸、将三甲基苯氧化为1,2,3-苯三甲酸、将正丁醛氧化为正丁酸、将丁烯醛氧化为丁烯酸、将丁烷氧化为乙酸乙酯、将丁烯氧化为马来酸酐、将丁烷氧化为马来酸酐、将苯氧化为马来酸酐或将丙烯氧化为丙烯酸。
在进一步有利的实施方案中,本发明方法可以用于将烃或醛氧化为酮、醇或醌,例如将芴氧化为芴酮、将三甲基苯酚氧化为三甲基苯醌、将乙醛氧化为乙酸酐、将萘氧化为萘醌、将蒽氧化为蒽醌、将对二异丙基苯氧化为氢醌、将对甲基异丙基苯氧化为甲酚或将烷属烃氧化为醇。
在进一步有利的实施方案中,本发明方法可以用于将醇氧化为醛或酮,例如将异丙醇氧化为丙酮、将仲丁醇氧化为甲基乙基酮或将甲醇氧化为甲醛。
在进一步有利的实施方案中,本发明方法可以用于将C-C单键氧化为C-C多键,例如将丁烯氧化为丁二烯、将乙基苯氧化为苯乙烯、将甲基环己烷氧化为甲苯或将丙烷氧化为丙烯。
在进一步有利的实施方案中,本发明方法可以用于将烃氧化为腈,例如用N2O将甲苯氧化为苄腈。
在进一步优选的实施方案中,本发明方法可以用于使用臭氧将C-C单键或C-C多键氧化以获得酸官能化物,例如将天然产物臭氧解为脂肪酸。
在进一步有利的实施方案中,本发明方法可以用于使用过氧化氢将C-C多键氧化以获得相应的二醇,例如由烯丙醇获得丙三醇。
所述烃可以以单组分的形式或以所述烃的混合物的形式使用。
在特别优选的实施方案中,所用的起始原料可以是环己烷。
在这种情况下中,有利的产物是环己醇、环己酮、氢过氧化环己基或其混合物,特别是环己醇、环己酮或其混合物。
根据本发明,用氧化剂将起始原料氧化。
在有利的实施方案中,所用氧化剂可以是含分子氧的气体,特别是分子氧。
所用的分子氧可以是三线态或单线态的双氧或三氧,即臭氧,优选双氧,特别是三线态的双氧,或这些分子形式的氧的混合物。含有这些分子氧的气体可以不含另外的组分。
含有这些分子氧的气体可以含有另外的不同的组分。
有用的另外的不同组分包括氧化气体,例如氮氧化物。
在另外的不同组分的情况下,在本发明方法中可以优选使用惰性气体,即在任何情况下都基本不参与氧化反应的那些气体,例如氮气(例如呈空气形式)或稀有气体(例如氩气)或其混合物。
在进一步优选的实施方案中,所用氧化剂可以是含有一种或多种氮氧化物的气体,特别是一种或多种氮氧化物。
有用的氮氧化物包括一氧化二氮、一氧化氮、二氧化氮和其混合物或低聚物。含有一种或多种这类氮氧化物的气体可以不含另外的组分。
含有一种或多种这类氮氧化物的气体可以含有另外的不同组分。
有用的另外的不同组分包括氧化性气体,例如氧气。
在另外的不同组分的情况下,有利的是,在本发明方法中使用惰性气体,即那些在任何情况下都基本上不参于氧化反应的气体,例如氮气(例如呈空气形式)或稀有气体(例如氩气)或其混合物。
在进一步优选的实施方案中,所用的氧化剂可以是在所述反应条件下为液体的化合物,例如过氧化物,如无机过氧化物,例如过氧化氢,或者有机过氧化物,例如氢过氧化环己烷、氢过氧化异丁基、氢过氧化异戊烯基、氢过氧化苯乙基、氢过氧化枯烯、氢过氧化1,2,3,4-四氢化萘或者过酸,例如过乙酸。
所用起始原料与含分子氧的气体中的分子氧的混合比例从化学的角度(例如由烷烃转化为醇或酮)和从工艺工程的角度(即所需的转化率)取决于起始原料转化为产物的所需转化程度,并且可容易地通过少许几个简单的预备实验最优化。
氧化剂和起始原料可以分开加入反应装置中。
氧化剂和起始原料可以在加入反应装置中之前部分混合,然后加入反应装置中。
氧化剂和起始原料可以在加入反应装置中之前全部混合,然后加入反应装置中。
根据本发明,氧化反应在反应装置中进行,所述反应装置具有位于下端的底部区域,位于上端的顶部区域和位于顶部区域和底部区域之间的反应区。
优选的反应装置为精馏塔,其描述在例如Kirk-Othmer,Encyclopediaof Chemical Technology(化学技术百科全书),第3版,第7卷,John Wiley& Sons,纽约,1979,第870-881页中,如板式塔,例如筛板塔或泡罩塔,或具有规整填料或乱堆填料的塔。
在优选的实施方案中,有用的塔板是便于反应混合物在塔中长时间停留的那些,例如浮阀塔板,优选泡罩塔盘或隧道罩塔盘。
在进一步优选的实施方案中,规整填料,例如织造的金属填料或片状金属填料,有利的是具有有序结构的那些,或者乱堆填料是可想到的。
在进一步优选的实施方案中,考虑使用滞留填料。这种滞留填料允许借助压力降调节反应区中的停留时间,并且即使在高负荷下也确保良好的分离性能。
在特别优选的实施方案中,可在用于将氧化剂供入反应装置中的最低进料点下方使用具有大量塔板数的内件,例如织造的金属填料或片状金属填料,有利的是具有有序结构的那些。
有利地,所述精馏塔应该具有10至100块,优选20至40块理论塔板的分离性能。
有利地,可以将两种反应物,即起始原料和氧化剂中较高沸点的反应物供入反应装置中,使其绝大部分或完全位于较低沸点反应物上面,特别是可以将较高沸点反应物供入精馏塔的上段,而将较低沸点反应物供入精馏塔的下段。
较高沸点反应物可以含有较低沸点反应物。
较低沸点反应物可以含有较高沸点反应物。
在特别优选的实施方案中,所述精馏塔在反应段和底部之间具有蒸馏段。
已经证明特别有利的是,在精馏塔的下段,即在蒸馏段中安装0至50块,优选5至30块理论塔板。
已经证明特别有利的是,在精馏塔的上段,即在反应区中安装0至50块,优选5至30块理论塔板。所述反应区可位于塔的精馏段内。
反应区可以位于塔的精馏段以外。
反应区可以位于精馏塔以外。
在这种情况下,反应区中的压力和精馏塔内的压力可以相同或不同。
图1表示反应装置的有利实施方案的示意图。在图1中:
1:反应段
2:蒸馏段
3:起始原料进料
4:催化剂进料
5:氧化剂,特别是气体氧化剂,例如空气的添加
6:气化器
7:产物料流
8:换热器
9:惰性气体排放
10:分离器
11:水排放
12:起始原料再循环
本发明方法优选可以优选在顺次连接的多个反应装置中进行。当在较低压力下操作下游反应装置时,可以有利地将在上游塔的蒸气料流中含有的部分能量转移到下游反应装置之一的进料料流中。
此外,可以有利地将部分未冷凝的蒸气料流循环进入反应装置的下段中。这种循环气体方法允许底部料流中存在的部分能量得以回收。
反应混合物在所述塔的塔板上的平均停留时间为1至120分钟,优选5至30分钟。
本发明方法,特别是当用环己烷作为起始原料时,可以优选在0.1至3.5Mpa,优选0.5至2.5Mpa的压力范围内进行,所述压力在反应装置底部区域测得。
然后,根据在反应区中将反应混合物保持为沸腾状态来考虑温度。通过少许几个简单的预备实验就可以容易地确定对于特定反应而言的适于此目的的温度。
当用环己烷作为起始原料时,反应区中的有利温度为70至220℃,优选120至190℃。
在进一步优选的实施方案中,反应装置可以具有位于上段的上端的用于回收气体的装置。
有利地,所述反应的进行应使得位于反应区下方的反应混合物被气化,得到液体和气体反应混合物的混合物。
在有利的实施方案中,在底部区域和反应区的区域中,反应装置充满液体反应混合物。
由于以这种方式获得的气体反应混合物与液体反应混合物相比密度较低,因此前者然后沿反应装置的顶部区域方向上升。归因于气相和液相间的相互作用,冷凝和气化过程可导致气相组成发生变化。
根据本发明,到达反应装置顶部区域的气体反应混合物被冷凝并由此供入反应区中,有利地以液相供入。
根据本发明,氧化剂以至少2,优选2至100,特别是2至50,更优选2至40,例如2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20股子料流引入反应区中。
氧化剂可以通过本身已知的方法,特别是用于将气体引入到液体中的方法引入反应装置中。
本发明方法可以在不加催化剂的条件下进行。
本发明方法可以在均相催化剂或非均相催化剂存在下进行。
当使用均相催化剂时,可有利地将其加入到位于反应装置顶部区域的反应混合物中,并随底部区域的反应混合物回收。
当使用非均相催化剂时,可有利地将其通过本身已知的方法固定在反应装置的反应区中。
通常而言,可将本身已知的催化剂用于特定的氧化反应中,例如将环己烷氧化成环己醇、环己酮或其混合物的情况下,使用钴盐或钴盐。
根据用于特定反应的这些催化剂的已知催化剂速率和本发明方法中选定的转化率,可以容易地确定催化剂的量,并且通过少许几个简单的预备实验就可以容易地最优化催化剂量。
有利地,包含产物的反应混合物可以在反应装置的底部区域取出,特别是当在反应条件下产物的沸点高于起始原料的沸点时。在底部区域取出的反应混合物可能由产物组成或者由除产物外,还包含另外组分,例如起始原料、副产物和第二产物的混合物组成。
有利地,含有产物的反应混合物可以在反应装置的顶部区域取出,特别是当在反应条件下产物的沸点低于起始原料的沸点时。在顶部区域取出的反应混合物可能由产物组成或者由除产物外,还包含另外组分,例如起始原料、副产物和第二产物的混合物组成。
当在本发明的氧化反应中水作为不可避免的或不期望的副产物或作为第二产物产生时,该水可以有利地在氧化反应期间从反应装置的反应区上方,有利地从塔顶排出。
对比例1
在分隔成八个室的泡罩塔反应器中,以使得液相在反应器中的停留时间为31分钟的方式调节在反应器的上端添加的环己烷料流。通过添加适量空气,该空气均匀分布在反应器各室上方,将环己烷的转化率设定为3.5%。反应器在16巴的压力下操作。
对环己醇、环己酮和氢过氧化环己烷的总选择性为83.9%。基于反应器中液相的时空产率为45.7kg/(m3*h)。
实施例1
基于液相的体积,将2415kg/(m3*h)环己烷供入反应塔的反应段的上方,所述反应塔在反应段(上)具有10块塔板和在蒸馏段(下)具有10块塔板。所述塔在11.9巴的压力下操作。引入0.15m3(STP)空气/千克环己烷,该空气均匀分布在所述塔的反应段的10块塔板上方。在基于200Wh/kg新鲜环己烷料流的气化器能量下,环己烷的转化率为10.1%。
对环己醇、环己酮和氢过氧化环己烷的总选择性为88.0%。基于反应器中液相的时空产率为250kg/(m3*h)。
对比例2
重复实施例1,不同之处在于将所有的空气以一股料流供入反应段的最低塔板。
环己烷的转化率为9.8%。
对环己醇、环己酮和氢过氧化环己烷的总选择性为84.1%。基于反应器中液相的时空产率为232kg/(m3*h)。
Claims (14)
1.一种用氧化剂氧化起始原料以获得产物的方法,其包括:
在反应装置中进行氧化反应,所述反应装置具有位于下端的底部区域,位于上端的顶部区域和位于顶部区域和底部区域之间的反应区;
在反应区中将反应混合物保持为沸腾状态;以及
将氧化剂以至少两股子料流引入反应区中。
2.权利要求1所述的方法,其中将离开反应区的未转化起始原料再循环入反应区中。
3.权利要求1或2所述的方法,其中所用起始原料为线性烷烃或环烷烃。
4.权利要求1至3中任一项所述的方法,其中所用氧化剂为在反应条件下为气体的氧化剂。
5.权利要求4所述的方法,其中所用氧化剂为含分子氧的气体。
6.权利要求1至5中任一项所述的方法,其中氧化反应在催化剂存在下进行。
7.权利要求1至6中任一项所述的方法,其中水在氧化反应中以副产物产生,并且该水在氧化反应期间从反应装置的反应区或顶部区域排出。
8.权利要求1至7中任一项所述的方法,其在10至300℃的温度下进行,所述温度在反应区中测得。
9.权利要求1至8中任一项所述的方法,其中所用反应装置为精馏塔。
10.权利要求1至9中任一项所述的方法,其中将起始原料用富含氧化剂的循环气体氧化。
11.权利要求1至10中任一项所述的方法,其中将含有产物的反应混合物在反应区的下方取出。
12.权利要求1至11中任一项所述的方法,其中将氧化剂和起始原料中的较高沸点反应物在氧化剂和起始原料中的较低沸点反应物的上面供入反应装置中。
13.权利要求1至12中任一项所述的方法,其中所用起始原料为环己烷。
14.权利要求1至13中任一项所述的方法,其中用空气氧化环己烷,在反应装置的底部区域连续取出反应混合物,从顶部区域连续排出未转化的环己烷和水,借助分相器分离环己烷和水并将得到的环己烷作为回流物供入反应装置的顶部区域。
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CN102766032A (zh) * | 2011-05-05 | 2012-11-07 | 中国石油化工股份有限公司 | 一种环己烷氧化的方法 |
CN102766031A (zh) * | 2011-05-05 | 2012-11-07 | 岳阳昌德化工实业有限公司 | 一种环己烷氧化的方法 |
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US20100249452A1 (en) * | 2007-10-22 | 2010-09-30 | Basf Se | Method for the oxidation of cycloaliphatic alcohols, cycloaliphatic ketones, or mixtures thereof with aqueous nitric acid and treatment of the dicarboxylic acids |
FR2955321B1 (fr) * | 2010-01-21 | 2012-02-10 | Rhodia Operations | Procede d'oxydation d'hydrocarbures |
US8936767B2 (en) * | 2010-01-29 | 2015-01-20 | Grupo Petrotemex. S.A. de C.V. | Oxidation system with sidedraw secondary reactor |
CN103596909B (zh) * | 2011-05-13 | 2015-08-26 | 艾菲纽技术公司 | 烷烃非均相催化气相氧化制备脂肪酮和/或其他含氧化合物 |
CN110922323A (zh) * | 2019-11-27 | 2020-03-27 | 天津东大化工集团有限公司 | 甲苯连续催化氧化生产苯甲酸热电耦合高效节能减排工艺 |
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DE1518255B1 (de) * | 1965-01-30 | 1969-12-11 | Vickers Zimmer Ag | Verfahren zur Aufarbeitung des Reaktionsgemisches der Oxydation von Cyclohexan mit sauerstoffhaltigen Gasen in fluessiger Phase |
US3957876A (en) * | 1970-07-31 | 1976-05-18 | E. I. Du Pont De Nemours And Company | Process for the oxidation of cyclohexane |
CA984855A (en) * | 1971-06-07 | 1976-03-02 | Hercules Incorporated | Production of aromatic secondary (c3-c7 alkyl) hydroperoxide |
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DE19643154A1 (de) * | 1996-10-18 | 1998-04-23 | Basf Ag | Verfahren zur Herstellung von Oxidationsprodukten des Cyclohexans im Gegenstrom |
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- 2003-07-30 BR BR0313572-1A patent/BR0313572A/pt not_active IP Right Cessation
- 2003-07-30 AU AU2003250195A patent/AU2003250195A1/en not_active Abandoned
- 2003-07-30 PL PL03375785A patent/PL375785A1/xx not_active Application Discontinuation
- 2003-07-30 WO PCT/EP2003/008407 patent/WO2004020083A1/de active Application Filing
- 2003-07-30 EP EP03790836A patent/EP1536885A1/de not_active Withdrawn
- 2003-07-30 CN CNA038205785A patent/CN1678389A/zh active Pending
- 2003-07-30 JP JP2004531837A patent/JP2005536341A/ja active Pending
- 2003-07-30 MX MXPA05001092A patent/MXPA05001092A/es not_active Application Discontinuation
- 2003-07-30 US US10/525,468 patent/US20050288532A1/en not_active Abandoned
- 2003-07-30 RU RU2005109150/04A patent/RU2346920C2/ru not_active IP Right Cessation
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2009
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102766032A (zh) * | 2011-05-05 | 2012-11-07 | 中国石油化工股份有限公司 | 一种环己烷氧化的方法 |
CN102766031A (zh) * | 2011-05-05 | 2012-11-07 | 岳阳昌德化工实业有限公司 | 一种环己烷氧化的方法 |
WO2012149827A1 (zh) * | 2011-05-05 | 2012-11-08 | 中国石油化工股份有限公司 | 一种氧化环己烷的方法 |
CN102766032B (zh) * | 2011-05-05 | 2014-10-01 | 中国石油化工股份有限公司 | 一种环己烷氧化的方法 |
US8940939B2 (en) | 2011-05-05 | 2015-01-27 | China Petroleum & Chemical Corporation | Process of oxidizing cyclohexane |
Also Published As
Publication number | Publication date |
---|---|
PL375785A1 (en) | 2005-12-12 |
JP2010018629A (ja) | 2010-01-28 |
EP1536885A1 (de) | 2005-06-08 |
DE10240816A1 (de) | 2004-03-11 |
RU2346920C2 (ru) | 2009-02-20 |
MXPA05001092A (es) | 2005-04-28 |
JP2005536341A (ja) | 2005-12-02 |
TW200404756A (en) | 2004-04-01 |
AU2003250195A1 (en) | 2004-03-19 |
KR20050037591A (ko) | 2005-04-22 |
US20050288532A1 (en) | 2005-12-29 |
RU2005109150A (ru) | 2005-08-10 |
WO2004020083A1 (de) | 2004-03-11 |
BR0313572A (pt) | 2005-06-21 |
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