CN112427047A - Method for large-scale preparation of urea-choline chloride green catalyst and solvent - Google Patents
Method for large-scale preparation of urea-choline chloride green catalyst and solvent Download PDFInfo
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- CN112427047A CN112427047A CN201910736755.0A CN201910736755A CN112427047A CN 112427047 A CN112427047 A CN 112427047A CN 201910736755 A CN201910736755 A CN 201910736755A CN 112427047 A CN112427047 A CN 112427047A
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Abstract
In order to overcome the technical defect that the mechanical dry mixing method is not suitable for large-scale preparation, the invention provides a method for preparing a urea-choline chloride green catalyst and a solvent in a large scale. Adding a commercially available 70% choline chloride aqueous solution and hydrogen bond donor urea into a reaction kettle according to a certain proportion, mixing, heating the obtained suspension to 70-80 ℃, simultaneously pumping a reaction system to a certain negative pressure state by using a vacuum pump, heating, stirring and dehydrating for a certain time; and raising the temperature of the dehydrated solution to 100-120 ℃, stirring and reacting for a certain time to obtain a uniform and transparent urea-choline chloride eutectic solvent product. Compared with the mechanical dry mixing method reported in the literature, the wet mixing method provided by the invention is easier to scale up the preparation and mass production.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for preparing a urea-choline chloride green catalyst and a solvent.
Background
The eutectic solvent is a novel green solvent similar to ionic liquid, and has wide application prospect in the fields of organic synthesis, bioactive compound extraction, nano material preparation, electrolyte and the like. The urea-choline chloride eutectic solvent is used as a non-acid and non-alkali catalyst, and can activate certain functional groups by forming hydrogen bonds with one or all reactants to promote the breaking and formation of chemical bonds. Research shows that the urea-choline chloride can catalyze a plurality of specific reactions, and the urea-choline chloride can play a role of sulfuric acid or sodium hydroxide in partial reactions, so that the process is expected to be green. In addition, the urea-choline chloride can also play a role of a solvent to dissolve or dilute certain reactants and promote the smooth reaction process. In some cases, the urea is the reaction raw material, and the effect of the urea-choline chloride is more remarkable. However, almost all research reports are in the pilot plant or micro-scale preparation stage, and the common description is that two or three dry hydrogen bond donor and hydrogen bond acceptor substances are mixed according to a certain proportion, then heated to about 80 ℃, and stirred for reaction for a period of time until clear liquid appears, and the eutectic solvent preparation is considered to be completed. We have found through a large number of experiments that this preparation condition is feasible for the preparation of small scale eutectic solvent samples. However, the preparation of large-scale products is not always feasible. At present, no report of large-scale industrial production of urea-choline chloride eutectic solvent products is found. According to the research result of a kilogram-level amplification process, the phenomenon that materials are not uniformly mixed in reaction often occurs during amplification preparation, and the obtained eutectic solvent product is crystallized after being placed for a period of time, so that the preparation is unsuccessful. When the preparation amount of a single kettle reaches more than kilogram level, the mixed mass transfer of two materials and the efficiency of forming hydrogen bonds are different from those of a small test. If a temperature of 80 ℃ is still used, no acceptable product is obtained no matter how long the stirring is carried out. The literature reports that eutectic solvents can be prepared by mechanical extrusion methods using mechanical force to convert to high temperatures and pressures, such as twin screw extruders or planetary ball mills, but also in small scale preparations. For this reason, it is necessary to search for a new production method and production equipment.
Although the urea-choline chloride eutectic solvent has wide application prospect. However, urea-choline chloride eutectic solvents are not available on the market at present. The main reason is that no enterprises have produced the urea-choline chloride eutectic solvent product. The literature reports preparation methods are almost exclusively in the laboratory research phase. We explore the preparation process of kilogram-level choline chloride series eutectic solvent products in the early period. From experimental results, it was found that improper preparation conditions or improper hydrogen bond donor to acceptor ratio can cause crystallization of the resulting eutectic solvent or even failure to achieve liquefaction. Through repeated groping and optimization of preparation conditions, a reaction and mass transfer rule in the amplification preparation process is found, and successful amplification preparation of the choline chloride series eutectic solvent is realized on a 20 kg-grade device. Through detection, the prepared eutectic solvent product reaches the level of a small-test prepared sample.
Most of the literatures report that the dried choline chloride and hydrogen bond donors such as urea are stirred and mixed at 80 ℃ until the mixture is in a transparent liquid state, namely the reaction is considered to be finished, and the preparation process of the eutectic solvent is finished. However, when the preparation is scaled up, the two materials are difficult to mix uniformly due to the increase of the material amount. If a temperature of 80 ℃ is still used, it is proved by experiments that it is difficult to obtain a homogeneous and stable liquid-like product even if the mass transfer effect is improved over a longer period of time and with more intensive stirring. It is believed that this is due to incomplete reaction of the two materials. Although increasing the temperature to 100 ℃ increases the reaction rate and yields acceptable products, the time required is too long and sometimes acceptable products are not obtained. It is considered that when the dehydrated choline chloride material is mixed with the urea hydrogen bond donor, the reaction efficiency is extremely low due to the fact that the solid is mixed with the solid, and formation of a hydrogen bond network of a eutectic solvent and uniformity of the hydrogen bond network are not facilitated. The preparation method comprises the steps of directly mixing 70% choline chloride aqueous solution and urea hydrogen bond donor, dehydrating the mixture under negative pressure in a liquid phase solution state, and then heating to enhance the reaction between the hydrogen bond donor and an acceptor to prepare the choline chloride-urea eutectic solvent product. Through repeated experimental research and optimization of a large number of parameters, the reaction condition and material proportion relation of 20 kg-grade amplified preparation is realized.
Disclosure of Invention
In order to solve the problems existing in the amplification preparation of the urea-choline chloride eutectic solvent, the invention provides a large-scale preparation method, namely, a choline chloride aqueous solution is directly mixed with hydrogen bond donor urea, negative pressure dehydration is carried out at about 80 ℃, and the mixture is heated to about 110-120 ℃ for continuous reaction, so that the urea-choline chloride eutectic solvent which does not crystallize for a long time and has stable quality can be prepared. This preparation condition has not been reported in any literature. This is what our invention is directed. The invention is different from the reported preparation method of the choline chloride-urea eutectic solvent, the choline chloride aqueous solution is directly mixed with the hydrogen bond donor urea without evaporating and drying the choline chloride aqueous solution, and the urea-choline chloride eutectic solvent is prepared in a large scale by adopting a post-dehydration mode. Through tests, the performance indexes of the prepared eutectic solvent, such as conductivity, viscosity and the like, are basically consistent with those reported in the literature.
The invention is implemented by adopting the following scheme:
a large-scale preparation method of a urea-choline chloride eutectic solvent is characterized by comprising the following steps: adding a commercially available choline chloride aqueous solution and hydrogen bond donor urea into a reaction kettle according to a certain proportion, mixing, heating the obtained suspension to more than 80 ℃ in the first step, pumping a reaction system to a negative pressure of about-0.4 MPa by using a vacuum pump, and stirring for about 2-3 hours; and then, in the second step, the temperature of the suspension or the solution is raised to about 110-120 ℃ and kept for about 4-6 hours, and a uniform and transparent urea-choline chloride eutectic solvent product is obtained. The concentration of the commercial choline chloride aqueous solution is about 75 percent. The urea is agricultural urea, and the biuret content is not higher than 0.5%. The temperature of the second step is between 110 ℃ and 120 ℃, and the holding time is 4-6 hours. The vacuum pump is a water jet vacuum pump, the negative pressure of the system is-0.3 to-0.5 MPa, and the stirring time is 1.5 to 3 hours. The reactor is a 316L stainless steel stirred tank reactor, the lining is polytetrafluoroethylene, and the stirring paddle is a polytetrafluoroethylene single paddle.
The invention has the following beneficial effects:
firstly, preparing a urea-choline chloride eutectic solvent product by directly mixing and stirring 70% choline chloride aqueous solution and hydrogen bond donor urea on a 20 kg-grade device; the eutectic solvent is simple to amplify and prepare, no waste water is discharged, and the obtained product has stable quality.
Drawings
FIG. 1 is a schematic diagram of a production apparatus and a process for preparing a urea-choline chloride eutectic solvent according to the present invention
1, stirring a reaction kettle; 2, a water storage tank; 3, a vacuum pump system; and 4, a product storage tank.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings.
Example 1
12 kg of 70% choline chloride aqueous solution and 7.5 kg of agricultural urea are directly added into a stirring reaction kettle 1, a jacket steam heating and vacuum pump system 3 is started until the system forms negative pressure of-0.4 MPa, the stirring and the dehydration are continued for 2 hours, and water evaporated from the materials enters a water storage tank 2. Then the negative pressure is removed, the temperature of the materials is raised to 115 ℃, and the materials are continuously stirred for 3 hours. And closing the steam for cooling, and putting the qualified product into the product storage tank 4.
The obtained eutectic solvent product has conductivity, density and viscosity of 0.199mS/cm and 1.240g/cm at 25 deg.C3And 660mpa.s and; DES water content measured by Karl Fischer method water content meter<0.32%。
Example 2
12 kg of 70% choline chloride aqueous solution and 7.5 kg of agricultural urea are directly added into a stirring reaction kettle 1, a jacket steam heating and vacuum pump system 3 is started until the system forms negative pressure of-0.3 MPa, the stirring and the dehydration are continuously carried out for 3 hours, and water evaporated from the materials enters a water storage tank 2. Then the negative pressure is removed, the temperature of the materials is raised to 120 ℃, and the materials are continuously stirred for 3 hours. And closing the steam for cooling, and putting the qualified product into the product storage tank 4.
The obtained eutectic solvent product has conductivity, density and viscosity of 0.202mS/cm and 1.235g/cm at 25 deg.C3And 620mpa.s and; DES water content measured by Karl Fischer method water content meter<0.51%。
Example 3
12 kg of 70% choline chloride aqueous solution and 7.5 kg of agricultural urea are directly added into a stirring reaction kettle 1, a jacket steam heating and vacuum pump system 3 is started until the system forms negative pressure of-0.5 MPa, stirring and dehydration are continuously carried out for 1.5 hours, and water evaporated from materials enters a water storage tank 2. Then the negative pressure is removed, the temperature of the materials is raised to 120 ℃, and the materials are continuously stirred for 2.5 hours. And closing the steam for cooling, and putting the qualified product into the product storage tank 4.
The obtained eutectic solvent product is detected, and the conductivity of the detected sample is measured at 25 DEG CThe density and the viscosity are respectively 0.208mS/cm and 1.206g/cm3And 650mpa.s and; DES water content measured by Karl Fischer method water content meter<0.46%。
Example 4
12 kg of 70% choline chloride aqueous solution and 7.5 kg of agricultural urea are directly added into a stirring reaction kettle 1, a jacket steam heating and vacuum pump system 3 is started until the system forms negative pressure of-0.4 MPa, stirring and dehydration are continuously carried out for 3 hours, and water evaporated from materials enters a water storage tank 2. Then the negative pressure is removed, the temperature of the materials is raised to 115 ℃, and the materials are continuously stirred for 4 hours. And closing the steam for cooling, and putting the qualified product into the product storage tank 4.
The obtained eutectic solvent product is detected that the conductivity, the density and the viscosity of a sample measured at 25 ℃ are respectively 0.211mS/cm and 1.218g/cm3And 750mpa.s and; DES water content measured by Karl Fischer method water content meter<0.38%。
Claims (6)
1. A method for preparing a urea-choline chloride green catalyst and a solvent in a large scale is characterized by comprising the following steps: the method comprises the following steps:
a. adding commercially available choline chloride aqueous solution and hydrogen bond donor urea into a reaction kettle according to a certain proportion, mixing, heating the obtained suspension to a certain temperature, pumping a reaction system to a certain negative pressure state by using a vacuum pump, and stirring for a certain time;
b. and (3) heating the dehydrated solution to a certain temperature, stirring and keeping for a certain time to obtain a uniform and transparent urea-choline chloride eutectic solvent product.
2. The method for preparing the urea-choline chloride green catalyst and solvent in a large scale according to claim 1, is characterized in that: the large-scale preparation refers to that the preparation amount of a single kettle reaches more than 20 kilograms, and the concentration of a commercial choline chloride aqueous solution is about 70-75%.
3. The method for preparing the urea-choline chloride green catalyst and solvent in a large scale according to claim 1 is characterized by comprising the following steps: the urea is agricultural urea, and the biuret content is not higher than 0.5%.
4. The method for preparing the urea-choline chloride green catalyst and solvent in a large scale according to claim 1 is characterized by comprising the following steps: the temperature after dehydration is between 110 ℃ and 120 ℃, preferably about 115 ℃, and the retention time is 3-12 hours.
5. The method for preparing the urea-choline chloride green catalyst and solvent in a large scale according to claim 1 is characterized by comprising the following steps: in the step a, the vacuum pump is a water jet vacuum pump, the negative pressure of the system is-0.3 MPa to-0.6 MPa, the stirring time is 1.0 to 5.0 hours, and the temperature of the material is 70 to 80 ℃.
6. The method for preparing the urea-choline chloride green catalyst and solvent in a large scale according to claim 1 is characterized by comprising the following steps: the reactor is a stainless steel stirred tank reactor with a jacket, the inside of the reactor is lined with polytetrafluoroethylene, the stirring paddle is made of polytetrafluoroethylene, and saturated steam is used for heating.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115368934A (en) * | 2022-07-05 | 2022-11-22 | 陕西建工安装集团 | Composite demulsifier and preparation process thereof |
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| WO2011060195A2 (en) * | 2009-11-11 | 2011-05-19 | Nuvo Research Inc. | Topical eutectic formulation |
| US20140083465A1 (en) * | 2011-06-22 | 2014-03-27 | Colgate-Palmolive Company | Liquid salt cleaning compositions |
| CN103710043A (en) * | 2013-12-30 | 2014-04-09 | 辽宁石油化工大学 | Method for removing sulfides by extraction with low-melting-point co-molten substance composed of urea and choline chloride |
| CN108186575A (en) * | 2018-03-14 | 2018-06-22 | 安徽工业大学 | It is a kind of based on eutectic solvent be solvent embedding system |
| CN109704389A (en) * | 2017-10-25 | 2019-05-03 | 孙剑波 | A method of ZnO nano-structure material is prepared using eutectic solvent |
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- 2019-08-10 CN CN201910736755.0A patent/CN112427047A/en active Pending
Patent Citations (5)
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| WO2011060195A2 (en) * | 2009-11-11 | 2011-05-19 | Nuvo Research Inc. | Topical eutectic formulation |
| US20140083465A1 (en) * | 2011-06-22 | 2014-03-27 | Colgate-Palmolive Company | Liquid salt cleaning compositions |
| CN103710043A (en) * | 2013-12-30 | 2014-04-09 | 辽宁石油化工大学 | Method for removing sulfides by extraction with low-melting-point co-molten substance composed of urea and choline chloride |
| CN109704389A (en) * | 2017-10-25 | 2019-05-03 | 孙剑波 | A method of ZnO nano-structure material is prepared using eutectic solvent |
| CN108186575A (en) * | 2018-03-14 | 2018-06-22 | 安徽工业大学 | It is a kind of based on eutectic solvent be solvent embedding system |
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| ZHEJIANG等: "Dissolution and regeneration of wool keratin in the deep eutectic solvent of choline chloride-urea", 《INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES》 * |
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| CN115368934A (en) * | 2022-07-05 | 2022-11-22 | 陕西建工安装集团 | Composite demulsifier and preparation process thereof |
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