CN110559806A

CN110559806A - Binary eutectic solvent and application thereof

Info

Publication number: CN110559806A
Application number: CN201910834948.XA
Authority: CN
Inventors: 黄宽; 李子良; 钟富裕; 蒋文静
Original assignee: Nanchang University
Current assignee: Nanchang University
Priority date: 2019-09-05
Filing date: 2019-09-05
Publication date: 2019-12-13

Abstract

The invention discloses a novel binary eutectic solvent and a method for preparing the same in NH₃And (4) application in trapping. The eutectic solvent is composed of A, B two components, wherein, A component is proton type ionic salt, B component is phenolic compound or imide compound. In the eutectic solvent provided by the invention, the component A is a hydrogen bond acceptor, the component B is a hydrogen bond donor, and both the component A, B have certain weak acidity which can be NH₃Provides a double active site. The eutectic solvent provided by the invention has NH₃Large absorption capacity, high selectivity, good cycle performance and low volatility, and is NH in industrial tail gas₃The separation and recovery of the (C) provides an efficient, green and environment-friendly absorbent.

Description

Binary eutectic solvent and application thereof

Technical Field

The invention relates to a novel binary eutectic solvent and the application of the eutectic solvent in NH₃The application of trapping and concentration, belonging to the field of green chemical industry.

Background

NH₃is a poisonous and harmful alkaline gas, which is a main driver for the formation of most secondary particles in PM2.5 and can react with acid gas (SO) in the atmosphere₂、NO_x) Secondary aerosol is generated by the reaction, thereby causing serious harm to the ecological environment. On the other hand, NH₃Can be used for producing ammonia water, nitrogenous fertilizer, ammonium salt, compound fertilizer, soda ash and the like, thereby being widely applied to the fields of chemical industry, light industry, pharmacy, chemical fertilizer and the like. Therefore, for NH in industrial exhaust gas₃The separation and the recycling have very important significance.

NH commonly used in industry₃The trapping method is acid washing method, and NH is absorbed by aqueous solution of inorganic acid (such as sulfuric acid, nitric acid, etc.)₃And finally concentrated to the corresponding ammonium salt. However, the aqueous solution of inorganic acid used in this method is highly corrosive, highly volatile, and absorbs NH₃Difficult to be desorbed and recycled, thereby generating a large amount of waste water. Compared with inorganic acid aqueous solution, the Ionic Liquid (ILs) is a novel green solvent, has the characteristics of wide liquid path, extremely low volatility, designable structure and the like, and recently, NH is generated in the solution₃The use of the trapping field has made great progress. However, the high viscosity and high cost of ionic liquids greatly hinder their large-scale industrial application. For this reason, there is an urgent need to develop an absorbent for NH, which is more efficient, has a simple preparation process, and has good regeneration properties₃And (4) trapping.

eutectic Solvents (DESs) are another new class of green solvents with similar characteristics to ionic liquids, also known as ionic liquid analogs. But compared with the ionic liquid, the eutectic solvent has simpler synthesis steps and lower cost. The eutectic solvent generally consists of two components, namely a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond donor generally comprises polyalcohol, carboxylic acid, amide and the like, and the hydrogen bond acceptor generally comprises quaternary ammonium salt, quaternary phosphonium salt and the like. Currently used for NH against eutectic solvents₃The research on trapping is still quite limited, the key being to obtain NH₃The eutectic solvent absorbent has large absorption capacity, high selectivity and good reversibility. The invention provides a novel binary eutectic solvent which is constructed by taking a proton type ionic salt as a hydrogen bond acceptor and taking a phenol compound or an imide compound as a hydrogen bond donor, wherein the proton type ionic salt and the phenol compound or the imide compound have certain weak acidity and can be NH₃The reversible chemical absorption provides double active sites, thereby realizing the NH in the industrial tail gas₃high efficiency of trapping.

Disclosure of Invention

The invention aims to provide a novel binary eutectic solvent, which consists of A, B two components, wherein the component A is a proton type ionic salt, and the component B is a phenolic compound or an imide compound.

The proton type ionic salt is specifically selected from one of ethylamine hydrochloride, triethylamine hydrochloride, imidazole hydrochloride, N, N, N ', N' -tetramethyl ethylenediamine dihydrochloride and N, N, N ', N' -tetramethyl-1, 3-propane diamine dihydrochloride, and the structural formula is as follows:

The phenolic compound or imide compound is specifically selected from one of phenol, resorcinol, phloroglucinol, succinimide, phthalimide and 1, 2-cyclohexane dicarboximide, and the structural formula is as follows:

In the binary eutectic solvent, the component A is a hydrogen bond acceptor, the component B is a hydrogen bond donor, and the molar ratio of the two components A, B is 1: 1 to 7. A, B components are mixed evenly according to a certain proportion to prepare the binary eutectic solvent of the invention.

The binary eutectic solvent can be used for synthesizing NH in tail gas discharged in ammonia industry and urea production process₃The principle of the high-efficiency trapping is that A, B two components have certain weak acidity, namely NH₃Provides a double active site. The binary eutectic solvent is used for NH₃The absorption temperature of the trapping is 25-100 ℃, the absorption pressure is 0.01-5 MPa, the desorption temperature is 75-150 ℃, and the desorption pressure is 0.0001-0.01 MPa.

The invention has the beneficial effects that: the binary eutectic solvent provided by the invention has NH₃Large absorption capacity, high selectivity, good cycle performance and low volatility. The binary eutectic solvent has cheap and easily obtained synthetic raw materials, simple preparation process and capability of trapping NH in industry₃The method has wide application prospect.

The specific implementation mode is as follows:

The present invention will be further illustrated by the following specific examples, but the present invention is not limited to the following examples.

Example 1

Weighing 1.63g (0.02mol) of ethylamine hydrochloride and 13.18g (0.14mol) of phenol in a flask, and stirring and mixing uniformly at 80 ℃ to prepare the binary eutectic solvent.

Example 2

2.03g (0.01mol) of N, N, N ', N' -tetramethyl-1, 3-propanediamine dihydrochloride and 4.71g (0.05mol) of phenol are weighed in a flask, and stirred and mixed uniformly at the temperature of 80 ℃ to prepare the binary eutectic solvent.

Example 3

Weighing 1.63g (0.02mol) of ethylamine hydrochloride and 15.41g (0.14mol) of resorcinol in a flask, and stirring and mixing uniformly at 80 ℃ to prepare the binary eutectic solvent.

Example 4

2.03g (0.01mol) of N, N, N ', N' -tetramethyl-1, 3-propanediamine dihydrochloride and 5.51g (0.05mol) of resorcinol are weighed into a flask, and are stirred and mixed uniformly at the temperature of 80 ℃ to prepare the binary eutectic solvent.

Example 5

Weighing 1.63g (0.02mol) of ethylamine hydrochloride and 17.66g (0.14mol) of phloroglucinol into a flask, and stirring and mixing uniformly at 80 ℃ to prepare the binary eutectic solvent.

Example 6

2.03g (0.01mol) of N, N, N ', N' -tetramethyl-1, 3-propanediamine dihydrochloride and 6.31g (0.05mol) of phloroglucinol are weighed into a flask and stirred and mixed uniformly at the temperature of 80 ℃ to prepare the binary eutectic solvent.

example 7

Weighing 2.75g (0.02mol) of triethylamine hydrochloride and 3.96g (0.04mol) of succinimide in a flask, and stirring and mixing uniformly at 80 ℃ to prepare the binary eutectic solvent.

Example 8

2.09g (0.02mol) of imidazole hydrochloride and 3.96g (0.04mol) of succinimide are weighed in a flask, and stirred and mixed uniformly at 80 ℃ to prepare the binary eutectic solvent.

Example 9

Weighing 2.75g (0.02mol) of triethylamine hydrochloride and 5.89g (0.04mol) of phthalimide in a flask, and stirring and mixing uniformly at 80 ℃ to prepare the binary eutectic solvent.

Example 10

2.09g (0.02mol) of imidazole hydrochloride and 5.89g (0.04mol) of phthalimide are weighed in a flask, and stirred and mixed uniformly at 80 ℃ to prepare the binary eutectic solvent.

Example 11

weighing 2.75g (0.02mol) of triethylamine hydrochloride and 9.19g (0.06mol) of 1, 2-cyclohexane dicarboximide into a flask, and stirring and mixing uniformly at 80 ℃ to prepare the binary eutectic solvent.

Example 12

2.09g (0.02mol) of imidazole hydrochloride and 9.19g (0.06mol) of 1, 2-cyclohexanedicarboximide are weighed into a flask and stirred and mixed evenly at 80 ℃ to prepare the binary eutectic solvent.

Example 13

3.78g (0.02mol) of N, N, N ', N' -tetramethylethylenediamine dihydrochloride and 7.53g (0.08mol) of phenol are weighed in a flask, and stirred and mixed uniformly at 80 ℃ to prepare the binary eutectic solvent.

Example 14

3.78g (0.02mol) of N, N, N ', N' -tetramethylethylenediamine dihydrochloride and 6.61g (0.06mol) of resorcinol are weighed into a flask and stirred and mixed uniformly at the temperature of 80 ℃ to prepare the binary eutectic solvent.

The density and viscosity of the eutectic solvents prepared in examples 1 to 6 at different temperatures are shown in tables 1 and 2, respectively:

TABLE 1 Density of eutectic solvents prepared in examples 1-6 at different temperatures

TABLE 2 viscosity of eutectic solvents prepared in examples 1 to 6 at different temperatures

10g of the eutectic solvent prepared in example 1, example 2 and example 3 was weighed and placed in an absorption cell, and NH was introduced at 40 ℃ under different pressures₃Stirring continuously, and calculating NH by the pressure change in the absorption cell after absorption is balanced₃The amount of absorption of (c). The results are shown in Table 3:

TABLE 3 eutectic solvents prepared in examples 1-6 for NH at 40 deg.C and different pressures₃Absorption amount of

Weighing 10g of the eutectic solvent prepared in example 1, placing the eutectic solvent in an absorption cell, and introducing NH with different pressures at 25 ℃, 40 ℃, 60 ℃ and 80 DEG₃Stirring continuously, and calculating NH by the pressure change in the absorption cell after absorption is balanced₃The results are shown in Table 4:

Table 4 eutectic solvents prepared in example 1 were applied to NH at different temperatures and pressures₃Absorption amount of

	0.01MPa	0.02MPa	0.05MPa	0.1MPa
					25℃	0.086g/g	0.123g/g	0.135g/g	0.171g/g
40℃	0.045g/g	0.056g/g	0.078g/g	0.101g/g
					60℃	0.046g/g	0.065g/g	0.089g/g	0.111g/g
80℃	0.022g/g	0.035g/g	0.061g/g	0.082g/g

Example 1, example 2 prepared eutectic solvent to NH at 40 ℃₃After the absorption is saturated, the mixture is heated to 80 ℃ and vacuumized to 0.0001MPa for desorptionThe desorption time was 2 h. After regeneration is finished, the eutectic solvent is measured again for NH at 40 ℃ and 0.1MPa₃The absorption amount was thus repeated 10 times, and the results are shown in Table 5:

Table 5 eutectic solvents prepared in examples 1 and 2 vs NH₃Cyclic absorption capacity of

The above data show that the eutectic solvent provided by the present invention is available for NH₃The repeated absorption effect is better.

TABLE 6 eutectic solvents prepared in examples 1 and 2 at 40 deg.C and 0.01MPa vs. NH₃/CO₂Ideal absorption selectivity of

	NH₃	CO₂	NH₃/CO₂
				Example 1	0.045g/g	0.00009g/g	500
Example 2	0.049g/g	0.00010g/g	490

The above data show that the eutectic solvent provided by the present invention is available for NH₃/CO₂Has excellent absorption selectivity.

Claims

1. A binary eutectic solvent, characterized in that: the eutectic solvent is composed of A, B, wherein the component A is proton type ionic salt, specifically selected from one of ethylamine hydrochloride, triethylamine hydrochloride, imidazole hydrochloride, N, N, N ', N' -tetramethyl ethylenediamine dihydrochloride and N, N, N ', N' -tetramethyl-1, 3-propane diamine dihydrochloride, and the component B is phenolic compound or imide compound, specifically selected from one of phenol, resorcinol, phloroglucinol, succinimide, phthalimide and 1, 2-cyclohexane dicarboximide.

2. The binary eutectic solvent of claim 1, characterized in that: the molar ratio of A, B two components in the eutectic solvent is 1: 1 to 7.

3. the binary eutectic solvent of claim 1 in NH₃And (4) application in trapping.

4. Use according to claim 3, characterized in that: NH (NH)₃The absorption temperature is 25-100 ℃ and the absorption pressure is 0.01-5 MPa in the trapping process.

5. Use according to claim 3, characterized in that: NH (NH)₃The desorption temperature in the trapping process is 75-150 ℃, and the desorption pressure is 0.0001-0.01 MPa.