CN105601609A - Method for using ionic liquid catalyst for catalyzing urea and propylene glycol to synthesize propylene carbonate - Google Patents
Method for using ionic liquid catalyst for catalyzing urea and propylene glycol to synthesize propylene carbonate Download PDFInfo
- Publication number
- CN105601609A CN105601609A CN201610131961.5A CN201610131961A CN105601609A CN 105601609 A CN105601609 A CN 105601609A CN 201610131961 A CN201610131961 A CN 201610131961A CN 105601609 A CN105601609 A CN 105601609A
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- CN
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- Prior art keywords
- catalyst
- propene carbonate
- reaction
- reactive distillation
- propane diols
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- 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.)
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000004202 carbamide Substances 0.000 title claims abstract description 23
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 17
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title abstract 12
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 title abstract 9
- 238000000066 reactive distillation Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 238000000746 purification Methods 0.000 claims abstract description 5
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 39
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 31
- -1 acrylic ester Chemical class 0.000 claims description 18
- 230000002194 synthesizing effect Effects 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910052752 metalloid Inorganic materials 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 5
- 239000000463 material Substances 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for using ionic liquid catalyst for catalyzing urea and propylene glycol to synthesize propylene carbonate. Ionic liquid is adopted to catalyze urea and propylene glycol to synthesize propylene carbonate. The process includes pre-reaction, propylene carbonate reactive distillation, catalyst separation and propylene carbonate purification. After being subjected to pre-reaction in a pre-reaction device (1), the ionic liquid, propylene glycol and urea are conveyed to a propylene carbonate reactive distillation column (2) for reactive distillation. Column reactor materials in the propylene carbonate reactive distillation column (2) are conveyed to a catalyst separator (3), light components are conveyed into a propylene carbonate purifying column (4) from the top to be purified, and the ionic liquid is recovered from the bottom. Ammonia gas at the top of the propylene carbonate reactive distillation column (2) is extracted and recovered.
Description
Technical field
The invention belongs to technical field prepared by propene carbonate, be specifically related to the method for ionic-liquid catalyst catalyzing urea and propane diols synthesizing acrylic ester.
Background technology
Propene carbonate (being called for short PC) is a kind of good organic solvent and important Organic chemical products, is widely used in the fields such as organic synthesis, gas separation, electrochemistry. Particularly synthesis of dimethyl carbonate via transesterification becomes the new growing point of propene carbonate in recent years. Owing to using a large amount of propane diols of production of propylene oxide dimethyl carbonate by-product, this has just caused the propane diols sales difficulty of production capacity surplus. So some researchers have transferred to sight on urea and propane diols synthesizing acrylic ester.
The catalyst that urea and propane diols synthesizing acrylic ester use in technique is in the past machine tin catalyst, metal oxide, hydrotalcite catalyst, slaine etc., these material catalytic efficiencies are not high, and separate and have difficulties in separation process, catalyst is easily separated out. Be difficult to recycle. And a kind of ionic-liquid catalyst catalyzing urea of our research and the method for propane diols synthesizing acrylic ester address this problem well.
Summary of the invention
The present invention is the method for ionic-liquid catalyst catalyzing urea and propane diols synthesizing acrylic ester, and while having solved urea and propane diols synthesizing acrylic ester, catalyst efficiency is low, the problem of catalyst recovery difficulty.
The technical solution adopted for the present invention to solve the technical problems is: the method for ionic-liquid catalyst catalyzing urea and propane diols synthesizing acrylic ester, adopts ionic liquid-catalyzed urea and propane diols synthesizing acrylic ester. Its technique comprises: pre-reaction, propene carbonate reactive distillation, catalyst separation, the purification of propene carbonate.
Described pre-reaction is: ionic liquid and propane diols are delivered into pre-reaction device (1), be 0.5h-6h preheating time, preheat temperature scope is 30 DEG C-100 DEG C, reach the backward pre-reaction device of temperature (1) and deliver into urea, pre-reaction temperature is 50 DEG C-200 DEG C, pre-reaction time is 0.1h-6h, and question response liquid reaches requirement and delivers into propene carbonate reactive distillation column (2).
Described propene carbonate reactive distillation is: pre-reaction feed liquid is delivered into propene carbonate reactive distillation column (2) from middle part, in reactive distillation processes, propane diols, propene carbonate and catalyst are that heavy constituent is shifted to tower reactor from the top of tower, the nitrogen that reaction generates is light component, separates from tower top. Reactive distillation temperature is 100-200 DEG C, tower reactor urea < 2wt%, and catalyst content is 0.1wt%-10wt%.
Described catalyst separation is: the heavy constituent that propane diols, propene carbonate and catalyst are contained in propene carbonate reactive distillation column (2) bottom, separating-purifying in catalyst separation device (3). The separation temperature of this device is 100 DEG C-230 DEG C, and separating pressure is 0MPa-5MPa. Ionic-liquid catalyst separates from the bottom of catalyst separation device (3), and reclaims and continue to participate in catalytic reaction, and propene carbonate and propane diols transfer out from catalyst separation device (3) top.
The purification of described propene carbonate is: the propane diols that catalyst separation device (3) top is separated and propene carbonate deliver into the purifying column (4) of propene carbonate from middle part. Propene carbonate is that heavy constituent part from tower moves into tower reactor, and when tower reactor propylene carbonate ester content reaches 99.9% output products when above, propane diols is that light component distillates from the top of tower, and reclaims and use as raw material. The operating temperature of this purifying column is 70 DEG C-200 DEG C.
The catalyst body that the present invention adopts ionic catalyst for containing zinc quasi-metal oxides and and containing zinc metalloid salt and quaternary ammonium salt is composite forms, its catalytic activity is high, and good separating effect, is well suited for industrial production.
Brief description of the drawings
Fig. 1 is the structural representation of the method for ionic-liquid catalyst catalyzing urea and propane diols synthesizing acrylic ester.
1--pre-reaction device in figure, 2--propene carbonate reactive distillation column, 3--catalyst separation device, 4--propene carbonate purifying column.
Detailed description of the invention
Example
Produce on the device of propene carbonate at a set of 5 kiloton urea methods, first ionic liquid and propane diols are delivered into pre-reaction device (1) preheating, reach the backward pre-reaction device of temperature (1) and deliver into urea, pre-reaction temperature is 50 DEG C-200 DEG C, pre-reaction time is 0.1h-6h, pre-reaction liquid delivers into pre-reaction feed liquid propene carbonate reactive distillation column (2) after reaching requirement from middle part, in reactive distillation processes, propane diols, propene carbonate and ionic-liquid catalyst are that heavy constituent is shifted to tower reactor from the top of tower, the nitrogen that reaction generates is light component, separate from tower top. reactive distillation temperature is 100-200 DEG C, tower reactor urea < 2wt%, and catalyst content is 0.1wt%-10wt%. the heavy constituent that propane diols, propene carbonate and catalyst are contained in propene carbonate reactive distillation column (2) bottom, separating-purifying in catalyst separation device (3). the separation temperature of this device is 100 DEG C-230 DEG C, and separating pressure is 0MPa-5MPa. ionic-liquid catalyst separates from the bottom of catalyst separation device (3), and reclaims and continue to participate in catalytic reaction, and propene carbonate and propane diols deliver into the purifying column (4) of propene carbonate from catalyst separation device (3) top. propene carbonate is that heavy constituent part from tower moves into tower reactor, and when tower reactor propylene carbonate ester content reaches 99.9% output products when above, propane diols is that light component distillates from the top of tower, and reclaims and use as raw material. the operating temperature of this purifying column is 70 DEG C-200 DEG C. it is still fine that catalyst is reused 100 catalytic effects.
Claims (6)
1. the method for ionic-liquid catalyst catalyzing urea and propane diols synthesizing acrylic ester, adopt ionic liquid-catalyzed urea and propane diols synthesizing acrylic ester, its technique comprises: pre-reaction, propene carbonate reactive distillation, catalyst separation, the purification of propene carbonate.
2. synthetic method as claimed in claim 1, it is characterized in that described pre-reaction is: ionic liquid and propane diols are delivered into pre-reaction device (1), be 0.5h-6h preheating time, preheat temperature scope is 30 DEG C-100 DEG C, reach the backward pre-reaction device of temperature (1) and deliver into urea, pre-reaction temperature is 50 DEG C-200 DEG C, and pre-reaction time is 0.1h-6h, and question response liquid reaches requirement and delivers into propene carbonate reactive distillation column (2).
3. synthetic method as claimed in claim 1, it is characterized in that described propene carbonate reactive distillation is: pre-reaction feed liquid is delivered into propene carbonate reactive distillation column (2) from middle part, in reactive distillation processes, propane diols, propene carbonate and catalyst are that heavy constituent is shifted to tower reactor from the top of tower, the nitrogen that reaction generates is light component, separates from tower top, and reactive distillation temperature is 100-200 DEG C, tower reactor urea < 2wt%, catalyst content is 0.1wt%-10wt%.
4. synthetic method as claimed in claim 1, it is characterized in that described catalyst separation is: the heavy constituent that propane diols, propene carbonate and catalyst are contained in propene carbonate reactive distillation column (2) bottom, separating-purifying in catalyst separation device (3), the separation temperature of this device is 100 DEG C-230 DEG C, separating pressure is 0MPa-5Mpa, ionic-liquid catalyst separates from the bottom of catalyst separation device (3), and reclaim and continue to participate in catalytic reaction, propene carbonate and propane diols transfer out from catalyst separation device (3) top.
5. synthetic method as claimed in claim 1, the purification that it is characterized in that described propene carbonate is: the propane diols that catalyst separation device (3) top is separated and propene carbonate deliver into the purifying column (4) of propene carbonate from middle part, propene carbonate is that heavy constituent part from tower moves into tower reactor, when tower reactor propylene carbonate ester content reaches 99.9% output products when above, propane diols is that light component distillates from the top of tower, and reclaim as raw material use, the operating temperature of this purifying column is 70 DEG C-200 DEG C.
6. synthetic method as claimed in claim 1, is characterized in that the present invention adopts the ionic catalyst of catalysis propene carbonate, and selecting catalyst main body is for containing zinc quasi-metal oxides with containing zinc metalloid salt and quaternary ammonium salt is composite forms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610131961.5A CN105601609A (en) | 2016-03-09 | 2016-03-09 | Method for using ionic liquid catalyst for catalyzing urea and propylene glycol to synthesize propylene carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610131961.5A CN105601609A (en) | 2016-03-09 | 2016-03-09 | Method for using ionic liquid catalyst for catalyzing urea and propylene glycol to synthesize propylene carbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105601609A true CN105601609A (en) | 2016-05-25 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610131961.5A Pending CN105601609A (en) | 2016-03-09 | 2016-03-09 | Method for using ionic liquid catalyst for catalyzing urea and propylene glycol to synthesize propylene carbonate |
Country Status (1)
| Country | Link |
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| CN (1) | CN105601609A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI642660B (en) * | 2017-07-19 | 2018-12-01 | 國立清華大學 | Method and apparatus for producing propylene carbonate and dimethyl carbonate |
| CN110156742A (en) * | 2019-07-02 | 2019-08-23 | 中国科学院过程工程研究所 | A kind of method that ionic liquid catalyzes urea and dibasic alcohol to synthesize cyclic carbonate |
Citations (4)
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|---|---|---|---|---|
| CN103420972A (en) * | 2013-08-01 | 2013-12-04 | 华东理工大学 | Method for continuously preparing propylene carbonate or ethylene carbonate |
| CN203329395U (en) * | 2013-04-22 | 2013-12-11 | 屈强好 | Pressure-reducing reaction rectifying device for producing propylene carbonate by urea method |
| CN203782064U (en) * | 2013-08-01 | 2014-08-20 | 江苏晋煤恒盛化工股份有限公司 | Reactor for synthesizing propylene carbonate or ethylene carbonate by utilizing urea and propylene glycol or ethylene glycol |
| CN104961720A (en) * | 2015-08-02 | 2015-10-07 | 何肖凤 | Preparation method of propylene carbonate |
-
2016
- 2016-03-09 CN CN201610131961.5A patent/CN105601609A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203329395U (en) * | 2013-04-22 | 2013-12-11 | 屈强好 | Pressure-reducing reaction rectifying device for producing propylene carbonate by urea method |
| CN103420972A (en) * | 2013-08-01 | 2013-12-04 | 华东理工大学 | Method for continuously preparing propylene carbonate or ethylene carbonate |
| CN203782064U (en) * | 2013-08-01 | 2014-08-20 | 江苏晋煤恒盛化工股份有限公司 | Reactor for synthesizing propylene carbonate or ethylene carbonate by utilizing urea and propylene glycol or ethylene glycol |
| CN104961720A (en) * | 2015-08-02 | 2015-10-07 | 何肖凤 | Preparation method of propylene carbonate |
Non-Patent Citations (1)
| Title |
|---|
| 刘春滟，李正军，张廷有: "离子液体在碳酸丙烯酯合成中的作用", 《皮革科学与工程》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI642660B (en) * | 2017-07-19 | 2018-12-01 | 國立清華大學 | Method and apparatus for producing propylene carbonate and dimethyl carbonate |
| CN110156742A (en) * | 2019-07-02 | 2019-08-23 | 中国科学院过程工程研究所 | A kind of method that ionic liquid catalyzes urea and dibasic alcohol to synthesize cyclic carbonate |
| CN110156742B (en) * | 2019-07-02 | 2020-12-04 | 中国科学院过程工程研究所 | A kind of method that ionic liquid catalyzes urea and dihydric alcohol to synthesize cyclic carbonate |
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