CN108912079A - A kind of method that fixed-bed catalytic prepares oxinane - Google Patents
A kind of method that fixed-bed catalytic prepares oxinane Download PDFInfo
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- CN108912079A CN108912079A CN201810825266.8A CN201810825266A CN108912079A CN 108912079 A CN108912079 A CN 108912079A CN 201810825266 A CN201810825266 A CN 201810825266A CN 108912079 A CN108912079 A CN 108912079A
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- Prior art keywords
- oxinane
- aqueous solution
- mixed liquor
- fixed bed
- fixed
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 229910016287 MxOy Inorganic materials 0.000 claims abstract description 12
- 230000018044 dehydration Effects 0.000 claims abstract description 12
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000003930 superacid Substances 0.000 claims abstract description 12
- 238000010792 warming Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of methods that fixed-bed catalytic prepares oxinane, include the following steps：1), Φ=4~6mm granular pattern SO is packed into the heat-insulating fixed bed reactors that diameter is 3.5cm, high 80cm4 2‑/MxOyClass solid super acid catalyst 200g；2) aqueous solution, is made into 1,5-PD and water, mixed liquor is made in mass concentration 50%-90%；3) fixed bed, is warming up to 180-320 DEG C of reaction；4) mixed liquor prepared, is pumped into reactor with mass space velocity 1.0-3.0g/min；5) aqueous solution containing oxinane, is obtained through dehydration, saltoutd, dried respectively, the component that rectifying collects when temperature is 87-89 DEG C can obtain oxinane product.In the present invention, by fixed bed reaction, realize the reaction of high-temperature moment, greatly reduce the generation of carbonized product, significantly improve the yield of reaction, can successive reaction, easy to operate, operational safety is high.
Description
Technical field
The present invention relates to the sides that oxinane preparation technical field more particularly to a kind of fixed-bed catalytic prepare oxinane
Method.
Background technique
In Patent No. " CN108148030A " open file, the method carbonization for preparing oxinane illustrated is serious,
By-product is more, and yield is low, intermittent reaction, and oxinane belongs to inflammable thing, and border ring distillation safety in side is low, the invention patent
By fixed bed reaction, realizes the reaction of high-temperature moment, greatly reduce the generation of carbonized product, mention the yield of reaction obviously
It is high.Fixed bed reaction is easily achieved serialization simultaneously, reduces the operation difficulty of reaction.
Summary of the invention
The purpose of the present invention is to solve disadvantages existing in the prior art, and a kind of fixed-bed catalytic preparation proposed
The method of oxinane.
To achieve the goals above, present invention employs following technical solutions：
A kind of method that fixed-bed catalytic prepares oxinane is designed, is included the following steps：
1), Φ=4~6mm granular pattern is packed into the heat-insulating fixed bed reactors that diameter is 3.5cm, high 80cm
SO4 2-/MxOyClass solid super acid catalyst 200g；
2) aqueous solution, is made into 1,5-PD and water, mixed liquor is made in mass concentration 50%-90%；
3) fixed bed, is warming up to 180-320 DEG C of reaction；
4) mixed liquor prepared, is pumped into reactor with mass space velocity 1.0-3.0g/min；
5) aqueous solution containing oxinane, is obtained through dehydration, saltoutd, dried respectively, it is 87-89 DEG C that temperature is collected in rectifying
When component can obtain oxinane product, after measured GC purity be 99.0-99.5%, molar yield 90-98%.
Preferably, the method that the fixed-bed catalytic prepares oxinane, includes the following steps：
1) the granular pattern SO of Φ=4mm, is packed into the heat-insulating fixed bed reactors that diameter is 3.5cm, high 80cm4 2-/
MxOyClass solid super acid catalyst 200g；
2) aqueous solution, is made into 1,5-PD and water, mixed liquor is made in mass concentration 70%；
3) fixed bed, is warming up to 180 DEG C of reactions；
4) mixed liquor prepared, is pumped into reactor with mass space velocity 1.8g/min；
5) aqueous solution containing oxinane, is obtained through dehydration, saltoutd, dried respectively, when rectifying collection temperature is 87 DEG C
Component can obtain oxinane product, after measured GC purity be 99.5%, molar yield 93%.
Preferably, the method that the fixed-bed catalytic prepares oxinane, includes the following steps：
1) the granular pattern SO of Φ=5mm, is packed into the heat-insulating fixed bed reactors that diameter is 3.5cm, high 80cm4 2-/
MxOyClass solid super acid catalyst 200g；
2) aqueous solution, is made into 1,5-PD and water, mixed liquor is made in mass concentration 90%；
3) fixed bed, is warming up to 240 DEG C of reactions；
4) mixed liquor prepared, is pumped into reactor with mass space velocity 1.5g/min；
5) aqueous solution containing oxinane, is obtained through dehydration, saltoutd, dried respectively, when rectifying collection temperature is 88 DEG C
Component can obtain oxinane product, after measured GC purity be 99.1%, molar yield 91%.
Preferably, the method that the fixed-bed catalytic prepares oxinane, includes the following steps：
1) the granular pattern SO of Φ=6mm, is packed into the heat-insulating fixed bed reactors that diameter is 3.5cm, high 80cm4 2-/
MxOyClass solid super acid catalyst 200g；
2) aqueous solution, is made into 1,5-PD and water, mixed liquor is made in mass concentration 50%；
3) fixed bed, is warming up to 260 DEG C of reactions；
4) mixed liquor prepared, is pumped into reactor with mass space velocity 2.6g/min；
5) aqueous solution containing oxinane, is obtained through dehydration, saltoutd, dried respectively, when rectifying collection temperature is 89 DEG C
Component can obtain oxinane product, after measured GC purity be 99.3%, molar yield 95%.
The method that a kind of fixed-bed catalytic proposed by the present invention prepares oxinane realizes high temperature by fixed bed reaction
Moment reaction is spent, the generation of carbonized product is greatly reduced, significantly improves the yield of reaction, while fixed bed reaction is easily achieved
Serialization reduces the operation difficulty of reaction, uses fixed bed reaction system in the present invention, is much larger than material using catalytic amount
Principle, keep reaction more thorough, using fixed bed reaction technique, realize moment reaction, reduce product and product and product
The time contacted with catalyst, side reaction are nearly no detectable, and the method for what the present invention announced prepare oxinane can be continuously anti-
It answers, easy to operate, operational safety is high.
Specific embodiment
It is next combined with specific embodiments below that the present invention will be further described.
Embodiment one
A kind of method that fixed-bed catalytic prepares oxinane, includes the following steps：
1) the granular pattern SO of Φ=4mm, is packed into the heat-insulating fixed bed reactors that diameter is 3.5cm, high 80cm4 2-/
MxOyClass solid super acid catalyst 200g；The catalyst is that patent No. ZL02151526.3 discloses catalyst；
2) aqueous solution, is made into 1,5-PD and water, mixed liquor is made in mass concentration 70%；
3) fixed bed, is warming up to 180 DEG C of reactions；
4) mixed liquor prepared, is pumped into reactor with mass space velocity 1.8g/min；
5) aqueous solution containing oxinane, is obtained through dehydration, saltoutd, dried respectively, when rectifying collection temperature is 87 DEG C
Component can obtain oxinane product, after measured GC purity be 99.5%, molar yield 93%.
Embodiment two
A kind of method that fixed-bed catalytic prepares oxinane, includes the following steps：
1) the granular pattern SO of Φ=5mm, is packed into the heat-insulating fixed bed reactors that diameter is 3.5cm, high 80cm4 2-/
MxOyClass solid super acid catalyst 200g；The catalyst is that patent No. ZL02151526.3 discloses catalyst；
2) aqueous solution, is made into 1,5-PD and water, mixed liquor is made in mass concentration 90%；
3) fixed bed, is warming up to 240 DEG C of reactions；
4) mixed liquor prepared, is pumped into reactor with mass space velocity 1.5g/min；
5) aqueous solution containing oxinane, is obtained through dehydration, saltoutd, dried respectively, when rectifying collection temperature is 88 DEG C
Component can obtain oxinane product, after measured GC purity be 99.1%, molar yield 91%.
Embodiment three
A kind of method that fixed-bed catalytic prepares oxinane, includes the following steps：
1) the granular pattern SO of Φ=6mm, is packed into the heat-insulating fixed bed reactors that diameter is 3.5cm, high 80cm4 2-/
MxOyClass solid super acid catalyst 200g；The catalyst is that patent No. ZL02151526.3 discloses catalyst；
2) aqueous solution, is made into 1,5-PD and water, mixed liquor is made in mass concentration 50%；
3) fixed bed, is warming up to 260 DEG C of reactions；
4) mixed liquor prepared, is pumped into reactor with mass space velocity 2.6g/min；
5) aqueous solution containing oxinane, is obtained through dehydration, saltoutd, dried respectively, when rectifying collection temperature is 89 DEG C
Component can obtain oxinane product, after measured GC purity be 99.3%, molar yield 95%.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (4)
1. a kind of method that fixed-bed catalytic prepares oxinane, which is characterized in that include the following steps：
1), Φ=4~6mm granular pattern SO is packed into the heat-insulating fixed bed reactors that diameter is 3.5cm, high 80cm4 2-/
MxOyClass solid super acid catalyst 200g；
2) aqueous solution, is made into 1,5-PD and water, mixed liquor is made in mass concentration 50%-90%；
3) fixed bed, is warming up to 180-320 DEG C of reaction；
4) mixed liquor prepared, is pumped into reactor with mass space velocity 1.0-3.0g/min；
5) aqueous solution containing oxinane, is obtained through dehydration, saltoutd, dried respectively, rectifying is collected when temperature is 87-89 DEG C
Component can obtain oxinane product, and GC purity is 99.0-99.5%, molar yield 90-98% after measured.
2. the method that a kind of fixed-bed catalytic according to claim 1 prepares oxinane, which is characterized in that including as follows
Step：
1) the granular pattern SO of Φ=4mm, is packed into the heat-insulating fixed bed reactors that diameter is 3.5cm, high 80cm4 2-/MxOy
Class solid super acid catalyst 200g；
2) aqueous solution, is made into 1,5-PD and water, mixed liquor is made in mass concentration 70%；
3) fixed bed, is warming up to 180 DEG C of reactions；
4) mixed liquor prepared, is pumped into reactor with mass space velocity 1.8g/min；
5) aqueous solution containing oxinane, is obtained through dehydration, saltoutd, dried respectively, group when temperature is 87 DEG C is collected in rectifying
Oxinane product can be obtained by dividing, and GC purity is 99.5% after measured, molar yield 93%.
3. the method that a kind of fixed-bed catalytic according to claim 1 prepares oxinane, which is characterized in that including as follows
Step：
1) the granular pattern SO of Φ=5mm, is packed into the heat-insulating fixed bed reactors that diameter is 3.5cm, high 80cm4 2-/MxOy
Class solid super acid catalyst 200g；
2) aqueous solution, is made into 1,5-PD and water, mixed liquor is made in mass concentration 90%；
3) fixed bed, is warming up to 240 DEG C of reactions；
4) mixed liquor prepared, is pumped into reactor with mass space velocity 1.5g/min；
5) aqueous solution containing oxinane, is obtained through dehydration, saltoutd, dried respectively, group when temperature is 88 DEG C is collected in rectifying
Oxinane product can be obtained by dividing, and GC purity is 99.1% after measured, molar yield 91%.
4. the method that a kind of fixed-bed catalytic according to claim 1 prepares oxinane, which is characterized in that including as follows
Step：
1) the granular pattern SO of Φ=6mm, is packed into the heat-insulating fixed bed reactors that diameter is 3.5cm, high 80cm4 2-/MxOy
Class solid super acid catalyst 200g；
2) aqueous solution, is made into 1,5-PD and water, mixed liquor is made in mass concentration 50%；
3) fixed bed, is warming up to 260 DEG C of reactions；
4) mixed liquor prepared, is pumped into reactor with mass space velocity 2.6g/min；
5) aqueous solution containing oxinane, is obtained through dehydration, saltoutd, dried respectively, group when temperature is 89 DEG C is collected in rectifying
Oxinane product can be obtained by dividing, and GC purity is 99.3% after measured, molar yield 95%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810825266.8A CN108912079A (en) | 2018-07-25 | 2018-07-25 | A kind of method that fixed-bed catalytic prepares oxinane |
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| CN201810825266.8A CN108912079A (en) | 2018-07-25 | 2018-07-25 | A kind of method that fixed-bed catalytic prepares oxinane |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1425500A (en) * | 2002-12-31 | 2003-06-25 | 曲阜师范大学 | Granular solid super strong acid catalyst and its preparing method |
| CN1473824A (en) * | 2003-08-01 | 2004-02-11 | 曲阜师范大学 | Method for catalytically synthesizing 1,4-dioxane using granular solid super strong acid |
| CN1793133A (en) * | 2006-01-09 | 2006-06-28 | 曲阜师范大学 | Process for catalyzing synthesizing tetrahydrofuran by granule type solid super strengthen acid |
| RU2644163C1 (en) * | 2016-08-17 | 2018-02-08 | Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук | Method for obtaining cyclic ethers from diols |
| CN108148030A (en) * | 2018-01-18 | 2018-06-12 | 迈奇化学股份有限公司 | A kind of method that 1,5- pentanediols cyclodehydration prepares oxinane |
-
2018
- 2018-07-25 CN CN201810825266.8A patent/CN108912079A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1425500A (en) * | 2002-12-31 | 2003-06-25 | 曲阜师范大学 | Granular solid super strong acid catalyst and its preparing method |
| CN1473824A (en) * | 2003-08-01 | 2004-02-11 | 曲阜师范大学 | Method for catalytically synthesizing 1,4-dioxane using granular solid super strong acid |
| CN1793133A (en) * | 2006-01-09 | 2006-06-28 | 曲阜师范大学 | Process for catalyzing synthesizing tetrahydrofuran by granule type solid super strengthen acid |
| RU2644163C1 (en) * | 2016-08-17 | 2018-02-08 | Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук | Method for obtaining cyclic ethers from diols |
| CN108148030A (en) * | 2018-01-18 | 2018-06-12 | 迈奇化学股份有限公司 | A kind of method that 1,5- pentanediols cyclodehydration prepares oxinane |
Non-Patent Citations (1)
| Title |
|---|
| ANIL WALI ET AL.: "Cyclodehydration of Some 1，n-Diols Catalysed by Sulfated Zirconia", 《J. CHEM. RESEARCH (S)》 * |
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Application publication date: 20181130 |