CN109593076A - A kind of application of KF/NaY catalyst in synthesizing ethylene carbonate - Google Patents
A kind of application of KF/NaY catalyst in synthesizing ethylene carbonate Download PDFInfo
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- CN109593076A CN109593076A CN201811476864.5A CN201811476864A CN109593076A CN 109593076 A CN109593076 A CN 109593076A CN 201811476864 A CN201811476864 A CN 201811476864A CN 109593076 A CN109593076 A CN 109593076A
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- ethylene carbonate
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- 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
- C07D317/38—Ethylene carbonate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of application of KF/NaY catalyst in synthesizing ethylene carbonate, this method carries out ester exchange reaction synthesizing ethylene carbonate using dimethyl carbonate and ethylene glycol as raw material, using KF/NaY as catalyst.This method is easy to operate, and catalyst efficiency is high, recycling is easy and multiplexing performance is good, and the production cost of ethylene carbonate can be effectively reduced.
Description
Technical field
The present invention relates to application of the molecular sieve catalyst in carbonate synthesis ester, more particularly, to a kind of KF/NaY catalyst
Application in synthesizing ethylene carbonate.
Background technique
Ethylene carbonate is a kind of heterocyclic ketone, also known as 1,3- dioxane pentanone or ethylene carbonate, diglycol carbonate
Ester, abbreviation EC, Nature comparison stablize, only in the presence of metal oxide, silica gel, active carbon 200 DEG C can just decompose.Carbonic acid
Vinyl acetate is the raw material of synthetic and surfactant, can be good at molten as the organic high boiling solvent of good polarity
Solve many polymer and resin.It is widely used in printing and dyeing, plastics, gas separation, Polymer Synthesizing as a kind of organic intermediate
And the fields such as electrochemistry, alternative ethylene oxide are used for ethoxylation, can be used as the raw material and use of synthesis furazolidone
Fibre trimmer, waterglass system slurry and processing agent of other fibers etc. are done, and is that carbonic acid two is generated by ester-interchange method
The primary raw material of methyl esters, polycarbonate, the high power lithium battery electrolyte as production high added value.In addition, using carbonic ester as base
The fatty poly-ester carbonate of this structural unit and it includes the copolymers of carbonate monomer as biodegradable material, oneself warp
Increasingly cause the attention of scientist.Ethylene carbonate is mainly used as eyeball synthetic fibre, polyamide fibre, polyester, the liquid that reels off raw silk from cocoons of polyvinyl chloride resin etc., choosing
Selecting property aromatic hydrocarbons extraction solvent, plastics and rubber intermediate foaming agent etc..It can be in addition, ethylene carbonate is the same with propene carbonate
Directly as sour gas (CO in de- natural gas2、H2S purifying solvent), and propylene phthalein can be replaced with ethylene carbonate
Amine, waterglass and urea system are referred and synthesized as soil quality stabilizing agent non-harmful in mixed mud engineering.Ethylene carbonate is widely used,
Referred to as century green basic chemical industry raw material, market potential are huge.
The synthetic method of ethylene carbonate mainly includes phosgenation, ester-interchange method, halohydrin method, ethylene oxide and CO2It closes
Cheng Fa, alcoholysis of urea.
Phosgenation is the method for earliest preparation of industrialization ethylene carbonate.The technique is directly anti-using ethylene glycol and phosgene
It answers, but it is there are complex process, yield are low, at high cost, and phosgene has severe toxicity and generates serious pollution to environment, at present
Gradually eliminated.
Ethylene oxide and CO2Synthetic method is ethylene oxide and CO2With quaternary ammonium salt, Dawson heteropolyacid salt, Schiff aluminium
Complex, metal phthalocyanine are the synthetic method of dominant catalyst, and advantage is by greenhouse gases CO2Fixed synthesis, but this is anti-
It should be volume-diminished reaction, condition of high voltage is conducive to the progress of reaction, so relatively severe condition is needed, including needing complexity
Catalyst and higher reaction pressure.
Halohydrin method is halohydrin and CO2(or HCO3 -) CH under catalyst3The method of product is generated in CN solvent.
Raw material needed for this method and catalyst price are higher, severe reaction conditions, and yield is lower.
Currently used preparation method is that ester exchange reaction obtains ethylene carbonate.By the ester of dimethyl carbonate and ethylene glycol
Exchange reaction and the method for preparing ethylene carbonate is exactly ester-interchange method.The method is from the point of view of process and uncomplicated, it is important to can look for
To suitable catalyst.At present in the ester exchange reaction of dimethyl carbonate and ethylene glycol, common catalyst has metallic sodium, alcohol
The homogeneous base catalyst such as sodium, the homogeneous acid catalysts such as sulfuric acid, hydrochloric acid, but these homogeneous catalysts suffer from product separation it is difficult,
Catalyst reuse rate is low, is also easy to produce acid-base waste fluid etc. is difficult to the shortcomings that improving.Therefore, there is an urgent need to find a kind of operation letter
Single, high catalytic efficiency, catalyst repeat performance is good, is easy recycling, and the side of the low synthesizing ethylene carbonate of production cost
Method.
Summary of the invention
The technical problem to be solved by the present invention is to exchange carbonate synthesis ethylene for current dimethyl carbonate and glycol ester
The problems such as catalyst usage amount occurred during ester is big and separation and recovery of catalyst is difficult, and product yield is low, provides a kind of behaviour
Make simply, high catalytic efficiency, catalyst easily recycles, and catalyst reusability is good, the side of the low synthesizing ethylene carbonate of production cost
Method.
To solve the above-mentioned problems, present invention employs technical solutions below:
The application of a kind of KF/NaY catalyst in synthesizing ethylene carbonate, it is characterised in that the KF/NaY catalyst is specific
It uses in the following way:
(1) dimethyl carbonate, ethylene glycol and KF/NaY catalyst are sequentially added in flask, wherein dimethyl carbonate and second
The molar ratio of glycol is 1:1~3:1；
(2) flask is put into oil bath, magnetic agitation heating, being warming up to temperature is 90~120 DEG C, is reacted at this temperature
2~6h；
(3) substance that step (2) obtains is cooled to room temperature, extracts reaction solution centrifuge separation, analyzed.
As limitation of the invention, KF/NaY catalyst amount of the present invention is the 3% of raw material quality of glycol
~9%.
KF/NaY catalyst of the present invention is prepared with the following method:
KF is dissolved in deionized water, NaY molecular sieve is added thereto, wherein the mass ratio of KF and NaY is 1:20-1:40
It is sufficiently stirred, impregnates at room temperature for 24 hours, then the dry 2h at 90 DEG C, is finally putting into Muffle furnace and roasts 6h at 550 DEG C, obtain
To KF/NaY catalyst.
The reaction equation of KF/NaY catalyst DMC and EG ester exchange reaction is as follows:
From reaction equation above it can be seen that KF/NaY first activates the hydroxyl on ethylene glycol, negative oxygen ion is formed, then
Carbon ion on attack dimethyl carbonate, is connected on dimethyl carbonate, then takes off a methoxyl group, forms double bond, later
Activated hydroxyl groups form negative oxygen ion to KF/NaY again, and attack carbon ion forms methoxyl group, product carbonic acid is obtained after demethoxylation
Vinyl acetate.
After above-mentioned technical solution, the present invention achieves the effect of highly significant, using KF/NaY as catalyst, in carbon
Energy consumption and cost are greatlyd save in the synthesis process of vinyl acetate, the reaction time is shorter, and catalyst amount reduces, catalyst
Performance is significant, and recycling using effect does not change significantly.
Detailed description of the invention
Fig. 1 are as follows: the CO before and after KF/NaY catalyst use2- TPD figure, wherein A is the CO before the use of KF/NaY catalyst2-
TPD figure, B are that KF/NaY catalyst uses the CO after 4 times2- TPD figure；
As seen from Figure 1, KF/NaY catalyst before and after use the quantity of basic sites, intensity there is no significant changes,
It can be seen that the catalyst has good stability in dimethyl carbonate and glycol ester exchange synthesizing ethylene carbonate process.
Specific embodiment
The present invention will be described further with regard to following embodiment, however, it should be noted that these embodiments are only to illustrate
It is used, and is not necessarily to be construed as the limitation that the present invention is implemented.
KF/NaY catalyst is prepared first:
(1) 0.2g KF is dissolved in 10mL deionized water, 4g NaY molecular sieve is added thereto, is sufficiently stirred, in room temperature
For 24 hours, then the dry 2h at 90 DEG C, is finally putting into Muffle furnace and roasts 6h at 550 DEG C lower dipping, obtains KF/NaY-1 catalysis
Agent.
(2) 0.16g KF is dissolved in 10mL deionized water, 4g NaY molecular sieve is added thereto, is sufficiently stirred, in room
For 24 hours, then the dry 2h at 90 DEG C, is finally putting into Muffle furnace at 550 DEG C and roasts 6h the lower dipping of temperature, obtains KF/NaY-2 catalysis
Agent.
(3) 0.13g KF is dissolved in 10mL deionized water, 4g NaY molecular sieve is added thereto, is sufficiently stirred, in room
For 24 hours, then the dry 2h at 90 DEG C, is finally putting into Muffle furnace at 550 DEG C and roasts 6h the lower dipping of temperature, obtains KF/NaY-3 catalysis
Agent.
(4) 0.1g KF is dissolved in 10mL deionized water, 4g NaY molecular sieve is added thereto, is sufficiently stirred, in room temperature
For 24 hours, then the dry 2h at 90 DEG C, is finally putting into Muffle furnace and roasts 6h at 550 DEG C lower dipping, obtains KF/NaY-4 catalysis
Agent.
The catalyst of preparation is used in following specific embodiments.
Embodiment 1
6mL dimethyl carbonate and 4mL ethylene glycol are added in flask, 0.134g KF/NaY-1 is catalyst, reaction temperature
It is 90 DEG C, reaction time 6h is reacted at this point in the reaction, and the yield of ethylene carbonate is 53.7%, is selectively
96.3%.
Embodiment 2
6mL dimethyl carbonate and 4mL ethylene glycol are added in flask, 0.268g KF/NaY-1 is catalyst, reaction temperature
It is 100 DEG C, reaction time 6h is reacted at this point in the reaction, and the yield of ethylene carbonate is 71.8%, is selectively
98.5%.
Embodiment 3
12mL dimethyl carbonate and 4mL ethylene glycol are added in flask, 0.268g KF/NaY-3 is catalyst, reaction temperature
Degree is 120 DEG C, and reaction time 4h is reacted at this point in the reaction, and the yield of ethylene carbonate is 62.7%, selectivity
It is 97.3%.
Embodiment 4
18mL dimethyl carbonate and 4mL ethylene glycol are added in flask, 0.4g KF/NaY-4 is catalyst, reaction temperature
It is 110 DEG C, reaction time 2h is reacted at this point in the reaction, and the yield of ethylene carbonate is 53.6%, is selectively
96.2%.
Embodiment 5
10mL dimethyl carbonate and 4mL ethylene glycol are added in flask, 0.3g KF/NaY-2 is catalyst, reaction temperature
It is 120 DEG C, reaction time 6h is reacted at this point in the reaction, and the yield of ethylene carbonate is 76.0%, is selectively
95.2%.
Embodiment 6
8mL dimethyl carbonate and 4mL ethylene glycol are added in flask, 0.2g KF/NaY-3 is catalyst, and reaction temperature is
120 DEG C, reaction time 4h is reacted at this point in the reaction, and the yield of ethylene carbonate is 71.9%, is selectively
96.5%.
Embodiment 7
18mL dimethyl carbonate and 4mL ethylene glycol are added in flask, 0.3g KF/NaY-3 is catalyst, reaction temperature
It is 120 DEG C, reaction time 6h is reacted at this point in the reaction.Catalyst is filtered after reaction, is washed,
It is as follows to reuse four evaluation results:
1. catalyst repeat performance evaluation result of table
As can be seen from the above table: KF/NaY catalyst has the ester exchange reaction of dimethyl carbonate and ethylene glycol good
Catalytic performance and stability.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (3)
1. a kind of application of KF/NaY catalyst in synthesizing ethylene carbonate, it is characterised in that the KF/NaY catalyst is specifically
It uses in the following way:
(1) dimethyl carbonate, ethylene glycol and KF/NaY catalyst are sequentially added in flask, wherein dimethyl carbonate and ethylene glycol
Molar ratio be 1:1~3:1；
(2) flask is put into oil bath, magnetic agitation heating, be warming up to temperature be 90~120 DEG C, at this temperature react 2~
6h；
(3) substance that step (2) obtains is cooled to room temperature, extracts reaction solution centrifuge separation, analyzed.
2. a kind of application of the KF/NaY catalyst according to claim 1 in synthesizing ethylene carbonate, it is characterised in that
The KF/NaY catalyst amount is the 3%~9% of raw material quality of glycol.
3. a kind of application of the KF/NaY catalyst according to claim 1 in synthesizing ethylene carbonate, it is characterised in that
The KF/NaY catalyst is prepared with the following method:
KF is dissolved in deionized water, NaY molecular sieve is added thereto, wherein the mass ratio of KF and NaY is that 1:20-1:40 is abundant
Stirring, impregnates for 24 hours at room temperature, and then the dry 2h at 90 DEG C, is finally putting into Muffle furnace and roasts 6h at 550 DEG C, obtain KF/
NaY catalyst.
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| CN201811476864.5A CN109593076A (en) | 2018-12-05 | 2018-12-05 | A kind of application of KF/NaY catalyst in synthesizing ethylene carbonate |
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| CN201811476864.5A CN109593076A (en) | 2018-12-05 | 2018-12-05 | A kind of application of KF/NaY catalyst in synthesizing ethylene carbonate |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304797A (en) * | 2000-06-21 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Catalyst carrying potassium oxide |
| CN1569811A (en) * | 2004-04-22 | 2005-01-26 | 宁夏大学 | Process for synthesizing dibutyl carbonate |
| CN101255115A (en) * | 2008-03-26 | 2008-09-03 | 中国科学院成都有机化学有限公司 | Method for synthesizing long-chain alkyl carbonate by transesterification |
| CN103030622A (en) * | 2013-01-15 | 2013-04-10 | 中国日用化学工业研究院 | Method for preparing glyceride carbonate by using loop reaction device |
-
2018
- 2018-12-05 CN CN201811476864.5A patent/CN109593076A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304797A (en) * | 2000-06-21 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Catalyst carrying potassium oxide |
| CN1569811A (en) * | 2004-04-22 | 2005-01-26 | 宁夏大学 | Process for synthesizing dibutyl carbonate |
| CN101255115A (en) * | 2008-03-26 | 2008-09-03 | 中国科学院成都有机化学有限公司 | Method for synthesizing long-chain alkyl carbonate by transesterification |
| CN103030622A (en) * | 2013-01-15 | 2013-04-10 | 中国日用化学工业研究院 | Method for preparing glyceride carbonate by using loop reaction device |
Non-Patent Citations (6)
| Title |
|---|
| AMIT KUMAR等: "《Promotion effect of coexistent hydromagnesite in a highly active solid base hydrotalcite catalyst for transesterifications of glycols into cyclic carbonates》", 《CATALYSIS TODAY》 * |
| MEI HONG等: "《An efficient and green transesterification of glycols into cyclic carbonates catalysed by KF/Ca–Mg–Al hydrotalcite》", 《JOURNAL OF CHEMICAL RESEARCH》 * |
| VELDURTHY, B等: "《Correlation between the basicity of solid bases and their catalytic activity towards the synthesis of unsymmetrical organic carbonates》", 《JOURNAL OF CATALYSIS》 * |
| 何茜等: "《制备条件对KF/MgO-Al2O3催化正丁醛自缩合反应性能的影响》", 《精细石油化工》 * |
| 潘赛勇等: "《碱性分子筛作用下甘油与碳酸二甲酯反应制碳酸甘油酯》", 《催化学报》 * |
| 辽宁省石油化学工业厅: "《辽宁化工产品大全》", 31 December 1994 * |
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