CN110256397A - The extracting method of biuret during urea and polyol reaction cyclic carbonate - Google Patents
The extracting method of biuret during urea and polyol reaction cyclic carbonate Download PDFInfo
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- CN110256397A CN110256397A CN201910671296.2A CN201910671296A CN110256397A CN 110256397 A CN110256397 A CN 110256397A CN 201910671296 A CN201910671296 A CN 201910671296A CN 110256397 A CN110256397 A CN 110256397A
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- biuret
- cyclic carbonate
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- polyol reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/189—Purification, separation, stabilisation, use of additives
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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
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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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Abstract
The present invention provides a kind of extracting methods of biuret during urea and polyol reaction cyclic carbonate, pass through evaporation, dissolution, heat filtering and crystallisation step, biuret sterling is obtained, realize catalyst simultaneously efficiently separates (catalyst recovery yield > 99.5%), the present invention extracts biuret from urea and polyol reaction liquid, it can be improved the rate of recovery of catalyst, to reduce catalyst circulation use cost；The extraction of high added value biuret can effectively improve the economy of entire technical process.Entire processing apparatus less investment, investment is low, biuret recovery efficiency is high, meets the practical metaplasia of industry and produces efficient, energy-efficient technical requirements.
Description
Technical field
The present invention relates to field of fine chemical, and in particular to during a kind of urea and polyol reaction cyclic carbonate
The extracting method of biuret.
Background technique
Cyclic carbonate (ethylene carbonate, propene carbonate, carbonic acid glyceride etc.) be it is a kind of application it is very extensive, quite by
Novel " green " organic compound paid attention to both at home and abroad.It specifically can be applied to extraction and separation, the organic synthesis of mixture
(polycarbonate synthesis resin, phenolic resin, degradable medical high molecular material), high energy density cells electrolyte, cosmetics
The fields such as additive and supercritical fluid isolation technics.
The common preparation method of cyclic carbonate be 1,3-PD, 1,2 propylene glycol and urea alcoholysis reaction, the technique by
In abundant raw material, urea is cheap, by-product generate ammonia can be used for the industrialized production of subsequent urea and study compared with
It is more.
Biuret is in urea production process, when temperature is higher than urea fusing point (150~170 DEG C), through deamination and condensation
React product generated.Meanwhile in urea crystals granulation process, a small amount of biuret also can be inevitably generated.Contracting two
Urea to the toxic effect of plant, thus usually in urea Biuret Content no more than 1%.
The fact that in view of about 0.8 wt% or so biuret is usually contained in urea, therefore, with urea and polyalcohol (second
Glycol, propylene glycol, glycerol) reaction prepares cyclic carbonate (ethylene carbonate, propene carbonate, carbonic acid glyceride etc.) process
In, the presence of biuret makes solution viscosity after reaction very big, low so as to cause catalyst filtration difficulty, the rate of recovery.So from
Biuret is extracted in urea and polyol reaction liquid, catalyst can not only be completely separated；And high added value biuret mentions
The economy that can make entire technical process is taken to increase.Up to now, the extraction in relation to biuret has not been reported.
Summary of the invention
The invention proposes a kind of extracting methods of biuret during urea and polyol reaction cyclic carbonate, instead
Should after the mixed liquor containing catalyst through evaporation, dissolution, filtering, crystallization, realize the same of high-quality biuret extraction
When, also obtain efficiently separating for catalyst.
Realize the technical scheme is that
The extracting method of biuret during urea and polyol reaction cyclic carbonate, steps are as follows:
(1) evaporation stage: the reaction solution of urea and polyalcohol enters evaporator, and evaporator upper gaseous phase obtains complete more of unreacted
Then first alcohol and cyclic carbonate etc. go to separate, evaporator lower part obtains evaporation product；
(2) course of dissolution: being transferred to dissolver for the evaporation product that step (1) obtains, and is then added solvent, to contracting under normal pressure
Two ureas and a small amount of polyalcohol and cyclic carbonate etc. are dissolved；
(3) heat filtering process: the lysate that step (2) is obtained is sent into heat filtering device, under normal pressure, is completely separated insoluble
Heterogeneous catalysis, lower part obtains filtrate；
(4) crystallization process: the filtrate that step (3) obtains enters crystallization apparatus, and biuret solid is obtained after crystallization, while obtaining molten
Liquid goes rectifying to separate.
Evaporimeter internal pressure is 15~150mmHg in the step (1), temperature is 150~220 DEG C, evaporation time 3
~12 h.
Solvent is at least one of water, ethyl alcohol or methanol in the step (2), and solution temperature is 80~170 DEG C, pressure
For condition of normal pressure.
Heat filtering temperature is 80~170 DEG C in the step (3).
Crystallization temperature is 0~25 DEG C in the step (4), and the time is 6~18 h.
Polyalcohol is ethylene glycol, propylene glycol or glycerol in the step (1).
Step (1) reaction solution includes catalyst, urea, biuret, cyclic carbonate and polyalcohol.
The beneficial effects of the present invention are: the present invention extracts biuret from urea and polyol reaction liquid, it can be improved and urge
The rate of recovery of agent, to reduce catalyst circulation use cost；The extraction of high added value biuret can effectively improve entire work
The economy of skill process.Entire processing apparatus less investment, investment is low, biuret recovery efficiency is high, meets the practical metaplasia of industry and produces
Efficiently, energy-efficient technical requirements.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is process flow chart of the invention.
Wherein, L1: catalyst, urea, biuret, cyclic carbonate, polyalcohol；L2: catalyst, biuret and a small amount of ring
Shape carbonic ester and polyalcohol；L3: solvent；L4: solvent, catalyst, biuret and a small amount of cyclic carbonate and polyalcohol；L5: molten
Agent, biuret and a small amount of cyclic carbonate and polyalcohol；L6: solvent and a small amount of cyclic carbonate, polyalcohol；E1: evaporator；
E2: dissolver；E3: heat filtering device；E4: crystallization apparatus；S1: catalyst；S2: biuret.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's every other embodiment obtained under that premise of not paying creative labor, belongs to this hair
The range of bright protection.
Embodiment 1
The present embodiment urea and ethylene glycol prepare the extraction of biuret during ethylene carbonate, and (catalyst uses zinc oxide and oxygen
Change calcium complexes, molar ratio 1:1), steps are as follows:
(1) evaporation stage: mixed liquor L1 enters evaporator E1, under conditions of pressure is 150 mmHg, 165 DEG C, 6 h, realizes
The products such as ethylene carbonate, hydroxyethyl carbamate, ethylene glycol steam from evaporator top and carry out next separation, steam
Hair device lower part obtains catalyst and without the organic matters such as boiling point biuret L2；
(2) course of dissolution: being transferred to dissolver E2 for above-mentioned L2 product, and solvent L3(water or ethyl alcohol is then added), in temperature
Biuret and a small amount of polyalcohol and cyclic carbonate etc. are dissolved under 80 DEG C of degree, normal pressure；
(3) heat filtering process: after dissolution, L4 enters heat filtering device E3, under 80 DEG C of temperature, normal pressure, is completely separated insoluble
The heterogeneous catalysis S1(catalyst of solution use zinc oxide and calcium oxide composite, molar ratio 1:1), obtained catalyst after
The continuous catalytic reaction process applied to urea and ethylene glycol, catalyst recovery yield 99.5%.Lower part obtains solution L5；
(4) crystallization process: L5 enters crystallization apparatus E4, under conditions of 0 DEG C of temperature, 18 h, normal pressure, is crystallized and is consolidated
Body product, as biuret S2, purity 98%, while obtaining solution L6 and rectifying is gone to separate.
Embodiment 2
The present embodiment urea and ethylene glycol prepare the extraction of biuret during ethylene carbonate, and (catalyst uses zinc oxide and oxygen
Change calcium complexes, molar ratio 1:1), steps are as follows:
(1) evaporation stage: the present invention prepares the extraction of biuret during propene carbonate for urea and propylene glycol.Evaporator
E1 realizes propene carbonate, hydroxypropyl carbamate, propylene glycol under conditions of pressure is 50 mmHg, 175 DEG C, 8 h
Equal products steam from evaporator top and carry out next separation.Remaining process such as 1 step of embodiment (1) is described；
(2) course of dissolution: being transferred to dissolver E2 for above-mentioned L2 product, and solvent L3(water or ethyl alcohol is then added), in temperature
Biuret and a small amount of polyalcohol and cyclic carbonate etc. are dissolved under 120 DEG C of degree, normal pressure；
(3) heat filtering process: after dissolution, L4 enters heat filtering device E3, under 120 DEG C of temperature, normal pressure, is completely separated insoluble
The heterogeneous catalysis S1(catalyst of solution use zinc oxide and calcium oxide composite, molar ratio 1:1), obtained catalyst after
The continuous catalytic reaction process applied to urea and ethylene glycol, catalyst recovery yield 99.5%.Lower part obtains solution L5；
(4) crystallization process: L5 enters crystallization apparatus E4, under conditions of 15 DEG C of temperature, 10 h, normal pressure, is crystallized and is consolidated
Body product, as biuret S2, while obtaining solution L6 and rectifying is gone to separate.
Embodiment 3
The present embodiment urea and ethylene glycol prepare the extraction of biuret during ethylene carbonate, and (catalyst uses zinc oxide and oxygen
Change calcium complexes, molar ratio 1:1), steps are as follows:
(1) evaporation stage: the present invention prepares the extraction of biuret during glycerol carbonate for urea and glycerol.Evaporator
E1, pressure be 15 mmHg, 220 DEG C, 12 h under conditions of, realize glycerol carbonate, 1,2- dihydroxypropyl amino carbonic ester,
The products such as glycerol steam from evaporator top and carry out next separation.Remaining process such as 1 step of embodiment (1) is described；
(2) course of dissolution: being transferred to dissolver E2 for above-mentioned L2 product, and solvent L3(water or ethyl alcohol is then added), in temperature
Biuret and a small amount of polyalcohol and cyclic carbonate etc. are dissolved under 170 DEG C of degree, normal pressure；
(3) heat filtering process: after dissolution, L4 enters heat filtering device E3, under 170 DEG C of temperature, normal pressure, is completely separated insoluble
The heterogeneous catalysis S1(catalyst of solution use zinc oxide and calcium oxide composite, molar ratio 1:1), obtained catalyst after
The continuous catalytic reaction process applied to urea and ethylene glycol, catalyst recovery yield 99.5%.Lower part obtains solution L5；
(4) crystallization process: L5 enters crystallization apparatus E4, under conditions of 25 DEG C of temperature, 6 h, normal pressure, is crystallized and is consolidated
Body product, as biuret S2, while obtaining solution L6 and rectifying is gone to separate.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. the extracting method of biuret during urea and polyol reaction cyclic carbonate, it is characterised in that steps are as follows:
(1) evaporation stage: the reaction solution of urea and polyalcohol enters evaporator, the separation of evaporator upper gaseous phase, evaporator lower part
Obtain evaporation product；
(2) course of dissolution: being transferred to dissolver for the evaporation product that step (1) obtains, and solvent is then added and is dissolved, obtains
To lysate；
(3) heat filtering process: the lysate that step (2) is obtained is sent into heat filtering device, obtains filtrate after filtering；
(4) crystallization process: the filtrate that step (3) obtains enters crystallization apparatus, and biuret solid is obtained after crystallization.
2. the extracting method of biuret during urea according to claim 1 and polyol reaction cyclic carbonate,
It is characterized by: evaporimeter internal pressure is 15~150 mmHg in the step (1), 150~220 DEG C of temperature, evaporation time are
3~12 h.
3. the extracting method of biuret during urea according to claim 1 and polyol reaction cyclic carbonate,
It is characterized by: solvent is at least one of water, ethyl alcohol or methanol in the step (2), solution temperature is 80~170 DEG C,
Pressure is condition of normal pressure.
4. the extracting method of biuret during urea according to claim 1 and polyol reaction cyclic carbonate,
It is characterized by: heat filtering temperature is 80~170 DEG C in the step (3).
5. the extracting method of biuret during urea according to claim 1 and polyol reaction cyclic carbonate,
It is characterized by: crystallization temperature is 0~25 DEG C in the step (4), the time is 6~18 h.
6. urea according to claim 1-5 is mentioned with biuret during polyol reaction cyclic carbonate
Take method, it is characterised in that: polyalcohol is ethylene glycol, propylene glycol or glycerol in the step (1).
7. urea according to claim 1-5 is mentioned with biuret during polyol reaction cyclic carbonate
Take method, it is characterised in that: step (1) reaction solution includes catalyst, urea, biuret, cyclic carbonate and polyalcohol.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910671296.2A CN110256397B (en) | 2019-07-24 | 2019-07-24 | Method for extracting biuret in process of preparing cyclic carbonate by reacting urea with polyhydric alcohol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910671296.2A CN110256397B (en) | 2019-07-24 | 2019-07-24 | Method for extracting biuret in process of preparing cyclic carbonate by reacting urea with polyhydric alcohol |
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| CN110256397A true CN110256397A (en) | 2019-09-20 |
| CN110256397B CN110256397B (en) | 2020-09-04 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111153833A (en) * | 2020-01-21 | 2020-05-15 | 山西中科惠安化工有限公司 | Method and device for extracting biuret from reaction liquid of urea and polyol |
| CN111185230A (en) * | 2020-01-21 | 2020-05-22 | 山西中科惠安化工有限公司 | Method for separating and recovering catalyst in reaction liquid of urea and polyalcohol |
Citations (3)
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|---|---|---|---|---|
| CN101735114A (en) * | 2009-12-17 | 2010-06-16 | 安徽泰格生物技术股份有限公司 | Purification method of biuret |
| CN105985310A (en) * | 2015-02-12 | 2016-10-05 | 屈强好 | Method for producing propylene carbonate from urea and 1,2-propylene glycol |
| CN105237439B (en) * | 2015-10-19 | 2017-10-13 | 大连理工大学 | A kind of method of Biuret Content in reduction industrial urea |
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2019
- 2019-07-24 CN CN201910671296.2A patent/CN110256397B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735114A (en) * | 2009-12-17 | 2010-06-16 | 安徽泰格生物技术股份有限公司 | Purification method of biuret |
| CN105985310A (en) * | 2015-02-12 | 2016-10-05 | 屈强好 | Method for producing propylene carbonate from urea and 1,2-propylene glycol |
| CN105237439B (en) * | 2015-10-19 | 2017-10-13 | 大连理工大学 | A kind of method of Biuret Content in reduction industrial urea |
Non-Patent Citations (1)
| Title |
|---|
| 蔡明招: "《实用工艺分析》", 31 August 1999, 华南理工大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111153833A (en) * | 2020-01-21 | 2020-05-15 | 山西中科惠安化工有限公司 | Method and device for extracting biuret from reaction liquid of urea and polyol |
| CN111185230A (en) * | 2020-01-21 | 2020-05-22 | 山西中科惠安化工有限公司 | Method for separating and recovering catalyst in reaction liquid of urea and polyalcohol |
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| CN110256397B (en) | 2020-09-04 |
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