CN109438177A - 一种环庚烷无催化剂氧化新方法 - Google Patents
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- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000003647 oxidation Effects 0.000 title claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 19
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims abstract description 32
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 15
- 239000001361 adipic acid Substances 0.000 claims abstract description 15
- QCRFMSUKWRQZEM-UHFFFAOYSA-N cycloheptanol Chemical compound OC1CCCCCC1 QCRFMSUKWRQZEM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000706 filtrate Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 17
- 238000010813 internal standard method Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 8
- 235000021050 feed intake Nutrition 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000005457 ice water Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- -1 cycloheptyl alkoxide Chemical class 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000036301 sexual development Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
- C07C27/10—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons
- C07C27/12—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons with oxygen
- C07C27/14—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons with oxygen wholly gaseous reactions
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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
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
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Abstract
一种环庚烷的无催化剂氧化方法,所述方法为:将环庚烷加到反应容器中,在100~160℃、O2压力0.8~2MPa的条件下反应3~48h,之后反应液经后处理,分离得到氧化产物庚二酸和己二酸、环庚醇、环庚酮;本发明涉及的环庚烷无催化剂氧化新方法操作简单,成本低,不使用催化剂,防止了氧化产品的过渡金属污染,并且该环庚烷氧化方法以清洁的O2为氧化剂,绿色环保。
Description
(一)技术领域
本发明涉及一种环庚烷无催化剂氧化新方法,属有机合成领域。
(二)背景技术
环庚烷催化氧化制备环庚醇和环庚酮是化学工业中一个重要的化学转化过程,环庚醇和环庚酮进一步氧化可以得到重要的中间体庚二酸,市场需求大。其中O2由于其价廉易得,原子经济性高等优点成为环庚烷催化氧化的最佳选择,但是目前以O2为氧化剂的环庚烷氧化体系往往使用催化剂促进反应进行,如金属配合物催化、金属纳米粒子催化、金属氧化物粒子催化、分子筛催化、碳材料催化、光促进催化、杂多酸催化、金属-有机骨架材料催化等。催化体系的使用,无疑会增加环庚烷氧化的成本,并且会造成附加的环境污染问题,不利于环庚烷氧化产物下游产品的大规模开发。无催化剂体系的开发,无疑有利于环庚烷催化氧化成本的降低,对拓展环庚烷氧化产物下游产品具有重要意义,同时对环境兼容性的环庚烷氧化体系的开发也具有重要意义。因此,本发明在无催化剂条件下氧化环庚烷,制备环庚醇、环庚酮、庚二酸和己二酸,不仅可以显著降低环庚烷催化氧化过程的成本,而且环境影响小,绿色环保,符合目前化学工业与生态环境兼容性发展的现实需求。
(三)发明内容
本发明的目的在于提供一种环庚烷无催化剂氧化新方法。
本发明的技术方案如下:
一种环庚烷的无催化剂氧化方法,所述方法为:
将环庚烷加到反应容器中,在100~160℃(优选130~150℃)、O2压力0.8~2MPa(优选1~1.6MPa)的条件下反应3~48h(优选6~12h),之后反应液经后处理,分离得到氧化产物庚二酸和己二酸、环庚醇、环庚酮;
具体的,所述后处理的方法为:反应结束后,待反应液冷却至室温(20~30℃),过滤,滤饼用环庚烷洗涤,并于60℃下真空干燥,得到庚二酸和己二酸(白色固体,HPLC分析确定庚二酸和己二酸的收率);滤液进行精馏,收集179~180℃的馏分为环庚酮,收集185~186℃的馏分为环庚醇,同时精馏回收未反应的环庚烷。
本发明反应容器可以为具有四氟乙烯内胆的不锈钢高压釜。
本发明的有益效果主要体现在:涉及的环庚烷无催化剂氧化新方法操作简单,成本低,不使用催化剂,防止了氧化产品的过渡金属污染,并且该环庚烷氧化方法以清洁的O2为氧化剂,绿色环保。
(四)具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此。
实施例1
在100mL具有四氟乙烯内胆的不锈钢高压釜中,投料50.0g环庚烷,封闭高压釜。搅拌缓慢升温到140℃,通入O2至1.2MPa,于140℃,1.2MPa O2压力下搅拌反应8.0h,冰水浴中搅拌冷却到室温。开启高压釜,将所得反应混合物过滤,所得固体经3×10mL环庚烷洗涤,60℃下真空干燥,所得白色固体HPLC分析,得庚二酸收率1.27%,己二酸收率0.35%。过滤所得滤液精馏,取179℃~180℃馏分,即为环庚酮,GC内标法分析得收率2.36%;取185℃~186℃馏分,即为环庚醇,GC内标法分析得收率0.98%;同时精馏回收未反应的环庚烷。
实施例2
在100mL具有四氟乙烯内胆的不锈钢高压釜中,投料50.0g环庚烷,封闭高压釜。搅拌缓慢升温到100℃,通入O2至1.2MPa,于100℃,1.2MPa O2压力下搅拌反应8.0h,冰水浴中搅拌冷却到室温。开启高压釜,将所得反应混合物过滤,所得固体经3×10mL环庚烷洗涤,60℃下真空干燥,所得白色固体HPLC分析,庚二酸收率0.0%,己二酸收率0.0%。过滤所得滤液精馏,取179℃~180℃馏分,即为环庚酮,GC内标法分析得收率0.04%;取185℃~186℃馏分,即为环庚醇,GC内标法分析得收率0.0%;同时精馏回收未反应的环庚烷。
实施例3
在100mL具有四氟乙烯内胆的不锈钢高压釜中,投料50.0g环庚烷,封闭高压釜。搅拌缓慢升温到160℃,通入O2至1.2MPa,于160℃,1.2MPa O2压力下搅拌反应6.0h,冰水浴中搅拌冷却到室温。开启高压釜,将所得反应混合物过滤,所得固体经3×10mL环庚烷洗涤,60℃下真空干燥,所得白色固体HPLC分析,得庚二酸收率1.77%,己二酸收率0.63%。过滤所得滤液精馏,取179℃~180℃馏分,即为环庚酮,GC内标法分析得收率0.74%;取185℃~186℃馏分,即为环庚醇,GC内标法分析得收率0.19%;同时精馏回收未反应的环庚烷。
实施例4
在100mL具有四氟乙烯内胆的不锈钢高压釜中,投料50.0g环庚烷,封闭高压釜。搅拌缓慢升温到140℃,通入O2至0.80MPa,于140℃,0.80MPa O2压力下搅拌反应8.0h,冰水浴中搅拌冷却到室温。开启高压釜,将所得反应混合物过滤,所得固体经3×10mL环庚烷洗涤,60℃下真空干燥,所得白色固体HPLC分析,得庚二酸收率0.96%,己二酸收率0.12%。过滤所得滤液精馏,取179℃~180℃馏分,即为环庚酮,GC内标法分析得收率2.05%;取185℃~186℃馏分,即为环庚醇,GC内标法分析得收率0.72%;同时精馏回收未反应的环庚烷。
实施例5
在100mL具有四氟乙烯内胆的不锈钢高压釜中,投料50.0g环庚烷,封闭高压釜。搅拌缓慢升温到140℃,通入O2至2.0MPa,于140℃,2.0MPa O2压力下搅拌反应8.0h,冰水浴中搅拌冷却到室温。开启高压釜,将所得反应混合物过滤,所得固体经3×10mL环庚烷洗涤,60℃下真空干燥,所得白色固体HPLC分析,得庚二酸收率0.89%,己二酸收率0.17%。过滤所得滤液精馏,取179℃~180℃馏分,即为环庚酮,GC内标法分析得收率1.96%;取185℃~186℃馏分,即为环庚醇,GC内标法分析得收率0.81%;同时精馏回收未反应的环庚烷。
实施例6
在100mL具有四氟乙烯内胆的不锈钢高压釜中,投料50.0g环庚烷,封闭高压釜。搅拌缓慢升温到140℃,通入O2至1.2MPa,于140℃,1.2MPa O2压力下搅拌反应3.0h,冰水浴中搅拌冷却到室温。开启高压釜,将所得反应混合物过滤,所得固体经3×10mL环庚烷洗涤,60℃下真空干燥,所得白色固体HPLC分析,得庚二酸收率0.58%,己二酸收率0.07%。过滤所得滤液精馏,取179℃~180℃馏分,即为环庚酮,GC内标法分析得收率0.67%;取185℃~186℃馏分,即为环庚醇,GC内标法分析得收率0.0%;同时精馏回收未反应的环庚烷。
实施例7
在100mL具有四氟乙烯内胆的不锈钢高压釜中,投料50.0g环庚烷,封闭高压釜。搅拌缓慢升温到140℃,通入O2至1.2MPa,于140℃,1.2MPa O2压力下搅拌反应48.0h,冰水浴中搅拌冷却到室温。开启高压釜,将所得反应混合物过滤,所得固体经3×10mL环庚烷洗涤,60℃下真空干燥,所得白色固体HPLC分析,得庚二酸收率1.45%,己二酸收率0.48%。过滤所得滤液精馏,取179℃~180℃馏分,即为环庚酮,GC内标法分析得收率1.36%;取185℃~186℃馏分,即为环庚醇,GC内标法分析得收率0.34%;同时精馏回收未反应的环庚烷。
实施例8
在100mL具有四氟乙烯内胆的不锈钢高压釜中,投料50.0g环庚烷,封闭高压釜。搅拌缓慢升温到140℃,通入O2至1.6MPa,于140℃,1.6MPa O2压力下搅拌反应12.0h,冰水浴中搅拌冷却到室温。开启高压釜,将所得反应混合物过滤,所得固体经3×10mL环庚烷洗涤,60℃下真空干燥,所得白色固体HPLC分析,得庚二酸收率1.33%,己二酸收率0.41%。过滤所得滤液精馏,取179℃~180℃馏分,即为环庚酮,GC内标法分析得收率1.56%;取185℃~186℃馏分,即为环庚醇,GC内标法分析得收率0.28%;同时精馏回收未反应的环庚烷。
Claims (5)
1.一种环庚烷的无催化剂氧化方法,其特征在于,所述方法为:
将环庚烷加到反应容器中,在100~160℃、O2压力0.8~2MPa的条件下反应3~48h,之后反应液经后处理,分离得到氧化产物庚二酸和己二酸、环庚醇、环庚酮。
2.如权利要求1所述的环庚烷的无催化剂氧化方法,其特征在于,反应温度为130~150℃。
3.如权利要求1所述的环庚烷的无催化剂氧化方法,其特征在于,O2压力为1~1.6MPa。
4.如权利要求1所述的环庚烷的无催化剂氧化方法,其特征在于,反应时间为6~12h。
5.如权利要求1所述的环庚烷的无催化剂氧化方法,其特征在于,所述后处理的方法为:反应结束后,待反应液冷却至室温,过滤,滤饼用环庚烷洗涤,并于60℃下真空干燥,得到庚二酸和己二酸;滤液进行精馏,收集179~180℃的馏分为环庚酮,收集185~186℃的馏分为环庚醇,同时精馏回收未反应的环庚烷。
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