CN111139035B

CN111139035B - Multi-substitution refrigerant and preparation method and application thereof

Info

Publication number: CN111139035B
Application number: CN201911378500.8A
Authority: CN
Inventors: 陈思廷
Original assignee: Individual
Current assignee: Individual
Priority date: 2019-12-27
Filing date: 2019-12-27
Publication date: 2021-11-02
Anticipated expiration: 2039-12-27
Also published as: CN111139035A

Abstract

The invention belongs to the technical field of refrigerants used for fixed refrigeration compressors, and particularly relates to a multi-substitution refrigerant and a preparation method and application thereof. The multi-substitution refrigerant (R-611) provided by the invention is suitable for subtropical climates, can substitute R-22, R-404, R-407, R-502 and R-507 refrigerants, has zero Ozone Depletion Potential (ODP) and extremely low temperature room effect (GWP), has the characteristics of environmental protection, high efficiency and energy conservation, and has a good market prospect.

Description

Multi-substitution refrigerant and preparation method and application thereof

Technical Field

The invention belongs to the technical field of refrigerants used for fixed refrigeration compressors, and particularly relates to a multi-substitution refrigerant and a preparation method and application thereof.

Background

In combination with the notice of 'green high-efficiency refrigeration action scheme' issued by the committee for national development and reform in 2019, the country seeks an advanced energy-saving technical product with green, environmental protection, high efficiency and energy conservation for the core requirement of coordination of green economy, circular economy and environmental protection.

According to the display of the energy data management center of the Ministry of industry and informatization, the electricity consumption of industrial refrigeration equipment accounts for 40% of the total energy consumption, the electricity consumption of commercial refrigeration equipment accounts for 70% of the total energy consumption, the product R-611 disclosed by the invention is applied to large-scale industrial and commercial refrigeration equipment, the average energy saving rate is more than 25%, and the economic benefit generated after energy-saving transformation is considerable. The R-611 product of the invention has the characteristic of complete compatibility with the original lubricating oil, so that the product becomes a unique technical product which can be put into use without replacing any brand of lubricating oil and adjusting, the advantage is particularly suitable for developing countries, and due to the multi-aspect limitation of economic capacity and the like, green refrigeration is urgently sought by various large-scale industries and businesses, and the problem of replacing new and old refrigeration equipment in developing countries is solved without adding extra investment.

Since the book of the protocol of montreal, various countries have been developing the research of energy-saving and environment-friendly refrigerants, and the substitute refrigerants proposed in this period are mainly considered to protect the ozone layer, and the development of HFCs refrigerants is one of the hot contents. However, after the book of the kyoto protocol is signed, people turn to pay attention to the protection of the ozone layer and the reduction of the greenhouse effect at the same time, and the ODP and the GWP of the refrigerant are required to be zero.

In recent years, the use of a large amount of fluorine-containing refrigeration working media such as CFC (chlorofluorocarbon) and HCFC (HCFC) causes serious damage to the earth ozone layer, and ozone holes or ozone depletion are found in the south and north poles. Along with the continuous development of economy, the usage amount of fluorine-containing refrigerant is continuously increased, and China becomes the largest ODS (ozone depletion substance) producing country and consuming country in developing China. If the ozone valley phenomenon is left to develop, the third ozone cavity of the world may appear above the world ridge, the Qinghai-Tibet plateau, after the south and the north poles, so that the ozone valley phenomenon brings great harm to human beings. After the Copenhagen world climate change peak meeting in 2009, the government of China officially approved the Copenhagen agreement and promises to immediately begin to execute the restrictive index of low carbon emission. According to the provisions of the Montreal protocol, HCFCs (hydrogen-containing chlorofluorocarbons) are completely forbidden in 1 month and 1 day in 2010 in China, the unit GDP energy consumption is required to be reduced by about 20%, and the total emission of main pollutants is required to be reduced by about 10%.

In order to effectively fulfill the international obligations of the natural refrigeration working medium and realize the fascinating international commitment of the natural refrigeration working medium, the natural refrigeration working medium which is green, environment-friendly, efficient and energy-saving is urgently required by China according to the core requirements of economic development, resource protection and ecological environment coordination in sustainable development. For our descendants, we have only one exit, which is: the production and use of ODS (ozone depletion substance) refrigerant were completely stopped, and green environment-friendly refrigerant was developed and used.

The largest power consumption in commercial projects is refrigeration equipment, which accounts for more than 70% of the total project power consumption, and the power consumption of office places and household air conditioners accounts for 85% of the total power consumption. Air conditioners which are produced in the market in China before 2016 and 6 months and have more than three-level energy efficiency belong to refrigeration equipment with high energy consumption and high pollution. The air conditioners which are environment-friendly and not energy-saving in China only occupy 5% of the total number of air conditioners, and the novel air conditioners cannot be replaced by national financial subsidies in the current economic state of China so as to meet the building energy-saving requirement.

Disclosure of Invention

In order to solve the defects of the prior art, the invention provides a multi-substitution refrigerant and a preparation method and application thereof. The multi-substitution refrigerant (R-611) provided by the invention is suitable for subtropical climates, has the refrigerant with zero Ozone Depletion Potential (ODP) and extremely low temperature room effect (GWP), has the characteristics of environmental protection, high efficiency and energy conservation, and has a good market prospect.

The technical scheme provided by the invention is as follows:

the multi-substitution type refrigerant comprises the following components in parts by weight: 10-30 parts of trifluoroiodomethane; 45-80 parts of propane; 15-40 parts of fluoroethane.

The multi-substitution refrigerant (R-611) provided by the invention takes a ternary mixture of trifluoroiodomethane (R13I1), fluoroethane (R161) and propane (R290) as the refrigerant, and the system performance is extremely excellent. The reason is as follows: because R290 has the characteristics of large latent heat, good heat-conducting property and the like, the unit cold quantity of R161 is large, the latent heat of the refrigerant can be improved, and the system operation efficiency is improved, and R290 has flammability, so that R13I1 is added for flame retardance and good matching is achieved.

Specifically, 20-25 parts of trifluoroiodomethane; 60-70 parts of propane; 20-25 parts of fluoroethane.

Specifically, 15-20 parts of trifluoroiodomethane; 65-75 parts of propane; 20-25 parts of fluoroethane.

Specifically, 10-15 parts of trifluoroiodomethane; 70-80 parts of propane; 15-25 parts of fluoroethane.

Specifically, 15-20 parts of trifluoroiodomethane; 55-65 parts of propane; 25-35 parts of fluoroethane.

Specifically, 25-30 parts of trifluoroiodomethane; 60-70 parts of propane; 15-25 parts of fluoroethane.

Specifically, 20-30 parts of trifluoroiodomethane; 45-55 parts of propane; 30-40 parts of fluoroethane.

The invention also provides a preparation method of the multi-substitution refrigerant, and the multi-substitution refrigerant is obtained by mixing the components in a vacuumized mixing tank according to the amount of the formula.

The technical scheme can be used for preparing and obtaining the multi-substitution refrigerant.

Specifically, the purity of each component is greater than or equal to 99.96 wt%.

The invention also provides application of the multi-substitution type refrigerant, which is used as a substitution refrigerant of the R-22 refrigerant, the R-404 refrigerant, the R-407 refrigerant, the R-502 refrigerant or the R-507 refrigerant.

The invention also provides application of the multi-substitution type refrigerant, which is used as a refrigerant of a commercial central air conditioner, a household split air conditioner, a central cold water system, a refrigeration house refrigerating system, a freezer fresh-keeping system, an air source heat pump hot water system, a constant temperature and humidity system or a food and pharmaceutical cold drying system.

In particular to a compressor for 1KW-500KW air-conditioning equipment and refrigeration house equipment.

The multi-substitution refrigerant provided by the invention is suitable for subtropical climates, has an R-611 refrigerant with zero Ozone Depletion Potential (ODP) and extremely low temperature room effect (GWP), and is suitable for commercial central air conditioners, central cold water systems, household central air conditioners, household split air conditioners, refrigeration storage refrigeration systems, ice chest preservation systems, air source heat pump hot water systems, constant temperature and humidity systems and food and pharmaceutical cold drying systems.

Compared with the prior art, the invention has the beneficial effects that:

1) the invention can be directly injected into or added into the original R-22, R-404, R-407, R-502 and R-507 refrigeration equipment at any time without replacing any part of the refrigeration equipment. The water solubility of propane, fluoroethane and trifluoroiodomethane in the refrigerant provided by the invention is small, the propane, fluoroethane and trifluoroiodomethane do not have chemical action with the lubricating oil in the original equipment, and the refrigerant is compatible with the lubricating oil in the original equipment, so that the refrigerant can be put into use without changing any original refrigeration equipment and lubricating oil and adjusting, and unnecessary economic loss caused to energy consumption units due to huge equipment waste caused by refrigerant replacement is avoided.

2) The refrigeration equipment provided by the invention directly replaces R-22, R-404, R-407, R-502 and R-507 and then is tested on original equipment, the refrigeration efficiency is high because the latent heat of evaporation is large and the cooling speed in unit time is higher, and the energy saving rate reaches 25-35% proved by three-year test data of R611 engineering research center, and the energy saving effect is good; the trifluoroiodomethane has better flame retardance and lower GWP value than R-22, so the refrigerant provided by the invention is non-inflammable, does not destroy the ozone layer, and does not generate the greenhouse effect.

3) The refrigerant provided by the invention has high refrigeration efficiency, so the charging amount is 60 percent of that of R-22, R-404, R-407, R-502 and R-507, and the operation is more portable.

4) The refrigerating capacity of the refrigerant provided by the invention is higher than that of R-22, R-404, R-407, R-502 and R-507 by more than 5-10 percent, so that the compressor can be unloaded in advance, and meanwhile, the refrigerant provided by the invention is a mixed refrigerant, the average molecular weight of which is 40 percent less than that of R-22, R-404, R-407, R-502 and R-507, the flowing property is better, the conveying pressure is low, the working pressure of the compressor is lightened, and the service life of the compressor can be effectively prolonged by early unloading and lightening of the working pressure.

5) The fixed refrigeration compressor provided by the invention has the advantages that the chemical properties of all components of the refrigerant are stable, and the refrigerant does not contain olefin with good chemical activity, so that the performance of the refrigerant is more stable.

Detailed Description

The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.

Example 1

The multi-substitution refrigerant is prepared by fully mixing the following raw materials in parts by weight: 22 parts of trifluoroiodomethane; 58 parts of propane; 20 parts of fluoroethane. The preparation method comprises the following steps:

s1, rectifying and purifying the three raw materials on a production line, wherein a rectifying tower meets the height and standard of 99.96% of refrigerant raw materials;

s2, detecting the purity of the three raw materials by using an agilent color plotter to ensure that the purity of the raw materials reaches 99.96 percent of a refrigerant level;

s3, connecting the full-automatic multifunctional microwave vacuum mixing tank, wherein the type of the full-automatic multifunctional microwave vacuum mixing tank is as follows; YDL-6000L;

s4, vacuumizing the full-automatic blending tank to reach a negative pressure state;

s5, adding the raw materials reaching the standard into a full-automatic mixing tank according to the weight part ratio, and specifically, closing a feeding valve, vacuumizing, opening the feeding valve after vacuumizing, and opening a feeding pump to feed the raw materials;

s6, starting the full-automatic blending device to stir for three hours;

s7, detecting the finished product, namely the mixed refrigerant after stirring for three hours, and detecting the accuracy of the weight part ratio of each component;

s8, pumping the mixed refrigerant into an automatic filling system, and filling the mixed refrigerant into a mixed pressure container to obtain a finished product, wherein a cleaning reagent is used for cleaning the mixed pressure container, the cleaning reagent is propane with the purity of more than 99.96 wt%, the mixed pressure container is vacuumized after the cleaning is finished, the absolute pressure in the mixed pressure container is reduced to be less than 0.15Pa, and then filling is carried out.

Example 2

The multi-substitution refrigerant is prepared by fully mixing the following raw materials in parts by weight: 15 parts of trifluoroiodomethane; 65 parts of propane; 20 parts of fluoroethane, the preparation method of which is the same as example 1.

Example 3

The multi-substitution refrigerant is prepared by fully mixing the following raw materials in parts by weight: 15 parts of trifluoroiodomethane; 70 parts of propane; 15 parts of fluoroethane, the preparation method of which is the same as example 1.

Example 4

The multi-substitution refrigerant is prepared by fully mixing the following raw materials in parts by weight: 20 parts of trifluoroiodomethane; 55 parts of propane; 25 parts of fluoroethane, the preparation method of which is the same as example 1.

Example 5

The multi-substitution refrigerant is prepared by fully mixing the following raw materials in parts by weight: 25 parts of trifluoroiodomethane; 60 parts of propane; 15 parts of fluoroethane, the preparation method of which is essentially the same as in example 1.

Example 6

The multi-substitution refrigerant is prepared by fully mixing the following raw materials in parts by weight: 15 parts of trifluoroiodomethane; 55 parts of propane; 30 parts of fluoroethane, the preparation method of which is substantially the same as in example 1.

The refrigerant prepared in example 6 was used as a test object, and the test was performed according to the related standard of the prior art, and the physical parameters thereof are shown in the following table 1:

TABLE 1

As can be seen from the above physical parameters, the refrigerant provided by the present invention has characteristics similar to those of R-22, R-404, R-407, R-502 and R-507, can replace R-22, R-404, R-407, R-502 and R-507, and has the following advantages: has small average molecular weight which is 60 percent of R-22, R-404, R-407, R-502 and R-507, does not destroy the ozone layer (ODP is zero) and does not cause greenhouse effect (GWP is less than 3).

The formula calculates the slip temperature under the standard atmospheric pressure to be 0.2301 ℃ and the slip temperature under the pressure of 3MPa to be 0.1087 ℃ according to the REFPROP model of the national Standard institute of standards, and the refrigerant can be regarded as an azeotrope-like refrigerant under the extremely small slip temperature.

The data of each parameter of R-611 and the theoretical circulation of each type of refrigerant at the evaporation temperature of 5 ℃ and the condensation temperature of 40 ℃ are calculated as the following table 2:

TABLE 2

In order to further illustrate the advantages of the refrigerant provided by the invention in the aspect of energy saving, the invention is illustrated in the concrete test content of the R611 engineering research center as an example. Two lattice force floor type heat pump units are installed in a laboratory of an engineering research center, wherein the numbers of the two lattice force floor type heat pump units are a first unit and a second unit, the first unit R-22, R-404, R-407, R-502 and R-507 are refrigerants, the refrigerants are alternately used every 6 months, the second unit is a novel energy-saving environment-friendly refrigerant R-611, and the two units have the same type, the same power and the same delivery date.

Now, two units (the refrigerants prepared in the embodiments 1 to 6 are put in) and the first unit (the refrigerants R-22, R-404, R-407, R-502 and R-507 are put in) are compared, and the compressors of the first unit and the second unit normally work for three years in total, so that the energy saving rate is calculated. Specific energy saving rate data are shown in tables 3 to 7 below:

TABLE 3 comparison of energy saving rates for R-22 and R-611

Group of	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
							Energy saving ratio (%)	33.42	31.11	28.87	29.70	27.72	26.29

TABLE 4 comparison of energy saving rates for R-404 and R-611

Group of	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
							Energy saving ratio (%)	31.11	28.51	27.81	29.11	28.20	27.11

TABLE 5 comparison of energy saving rates for R-407 and R-611

TABLE 6 comparison of energy saving rates for R-502 and R-611

Group of	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
							Energy saving ratio (%)	32.45	29.50	28.81	30.71	30.89	29.91

TABLE 7 comparison of energy saving rates for R-507 and R-611

Group of	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
							Energy saving ratio (%)	35.10	34.50	31.17	30.26	31.29	29.91

From the data, the multi-substitution refrigerant provided by the invention has the advantage that the operation energy consumption is obviously reduced compared with that of R-22, R-404, R-407, R-502 and R-507 refrigerants.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims

1. The multi-substitution refrigerant is characterized by being prepared by fully mixing the following raw materials in parts by weight: 22 parts of trifluoroiodomethane; 58 parts of propane; 20 parts of fluoroethane.

2. The multi-substitution refrigerant is characterized by being prepared by fully mixing the following raw materials in parts by weight: 15 parts of trifluoroiodomethane; 65 parts of propane; 20 parts of fluoroethane.

3. The multi-substitution refrigerant is characterized by being prepared by fully mixing the following raw materials in parts by weight: 15 parts of trifluoroiodomethane; 70 parts of propane; and 15 parts of fluoroethane.

4. The multi-substitution refrigerant is characterized by being prepared by fully mixing the following raw materials in parts by weight: 20 parts of trifluoroiodomethane; 55 parts of propane; 25 parts of fluoroethane.

5. The multi-substitution refrigerant is characterized by being prepared by fully mixing the following raw materials in parts by weight: 25 parts of trifluoroiodomethane; 60 parts of propane; and 15 parts of fluoroethane.

6. The multi-substitution refrigerant is characterized by being prepared by fully mixing the following raw materials in parts by weight: 15 parts of trifluoroiodomethane; 55 parts of propane; and 30 parts of fluoroethane.

7. A method of preparing a multi-replacement refrigerant according to any one of claims 1 to 6, wherein: and mixing the components in a vacuumized mixing tank according to the amount of the formula to obtain the multi-substitution refrigerant.

8. Use of a multi-replacement refrigerant according to any one of claims 1 to 6, wherein: as a substitute refrigerant for the R-22 refrigerant, the R-404 refrigerant, the R-407 refrigerant, the R-502 refrigerant, or the R-507 refrigerant.

9. Use of a multi-replacement refrigerant according to any one of claims 1 to 6, wherein: the refrigerant is used as a refrigerant of a commercial central air conditioner, a household split air conditioner, a central cold water system, a cold storage refrigeration system, a freezer fresh-keeping system, an air source heat pump hot water system, a constant temperature and humidity system or a food and pharmaceutical cold drying system.