Refrigerant-containing composition, use thereof, refrigerator using same, and method for operating refrigerator
阅读说明：本技术 含有制冷剂的组合物、其用途以及使用其的冷冻机和该冷冻机的运转方法 (Refrigerant-containing composition, use thereof, refrigerator using same, and method for operating refrigerator ) 是由 板野充司 加留部大辅 四元佑树 大久保瞬 高桑达哉 于 2020-04-16 设计创作，主要内容包括：本发明所要解决的技术问题在于：提供一种兼具具有与R410A同等的冷冻能力、GWP充分小并且按照美国采暖冷冻空调学会(ASHRAE)的标准为微燃性(2L级)这三种性能的制冷剂组合物。本发明解决技术问题的方法在于：提供一种含有制冷剂的组合物,上述制冷剂以特定混合比例含有CO-(2)以及反式－1,2－二氟乙烯(HFO-1132(E))、二氟甲烷(R32)和2,3,3,3－四氟－1－丙烯(R1234yf)。(The technical problem to be solved by the invention is as follows: provided is a refrigerant composition having three performances of a refrigerating capacity equivalent to R410A, a sufficiently low GWP, and a low combustibility (class 2L) according to the American society for heating, refrigerating and air-conditioning (ASHRAE). The method for solving the technical problem of the invention comprises the following steps: disclosed is a composition containing a refrigerant containing CO at a specific mixing ratio 2 And trans-1, 2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), and 2,3,3, 3-tetrafluoro-1-propene (R1234 yf).)
1. A refrigerant-containing composition characterized by:
the refrigerant contains CO2And trans-1, 2-difluoroethylene (HFO-1132(E)), difluoromethane (R32) and 2,3,3, 3-tetrafluoro-1-propene (R1234yf), and reacting CO2And R32, HFO-1132(E) and R1234yf are w and x, y and z, respectively, where the total of R32, HFO-1132(E) and R1234yf is (100-w) mass% in the composition diagram of 3 components,
when w is more than 0 and less than or equal to 1.2, the coordinates (x, y, z) are within the range of a graph formed by connecting 7 points of the point I, the point J, the point K, the point L, the point B ', the point D and the point C respectively, the curve JJ, the curve JK, the curve KL, the straight line LB', the straight line B ', the straight line DC and the straight line CI or on the line segment, wherein the points on the straight line B' D and the straight line CI are not included,
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point L (51.7,28.9, 19.4-w),
Point B "(-1.5278 w)2+2.75w+50.5,0.0,1.5278w2－3.75w+49.5)、
Point D (-2.9167 w +40.317,0.0,1.9167w +59.683),
Point C (0.0, -4.9167 w +58.317,3.9167w + 41.683);
when w is more than 1.2 and less than or equal to 4.0, the coordinates (x, y, z) are within the range of a graph formed by connecting 7 points of the point I, the point J, the point K, the point L, the point B, the point D and the point C, the curve JJ, the curve JK, the curve KL, the straight line LB, the straight line B 'D, the straight line DC and the straight line CI or on the line segment, wherein the points on the straight line B' D and the straight line CI are not included,
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point L (51.7,28.9, 19.4-w),
Point B "(51.6,0.0, 48.4-w),
Point D (-2.8226 w +40.211,0.0,1.8226w +59.789),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w+41.553)；
When w is more than 4.0 and less than or equal to 7.0, the coordinates (x, y, z) are within the range of a graph formed by connecting 7 points of the point I, the point J, the point K, the point L, the point B ', the point D and the point C, the curve IJ, the curve JK, the curve KL, the straight line LB', the straight line B ', the straight line DC and the straight line CI or on the line segment, wherein the points on the straight line B' D and the straight line CI are not included,
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point L (51.7,28.9, 19.4-w),
Point B "(51.6,0.0, 48.4-w),
Point D (-2.8 w +40.1,0.0,1.8w +59.9),
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w+41.7)，
And the number of the first and second electrodes,
curve IJ is represented by coordinates (x,0.0236 x)2－1.716x+72,－0.0236x2+0.716x + 28-w) represents,
curve JK consists of coordinates (x,0.0095 x)2－1.2222x+67.676,－0.0095x2+0.2222x + 32.324-w),
the curve KL is represented by the coordinates (x,0.0049 x)2－0.8842x+61.488,－0.0049x2-0.1158 x + 38.512-w.
2. A refrigerant-containing composition characterized by:
the refrigerant contains CO2And trans-1, 2-difluoroethylene (HFO-1132(E)), difluoromethane (R32) and 2,3,3, 3-tetrafluoro-1-propene (R1234yf), and reacting CO2And R32, HFO-1132(E) and R1234yf are w and x, y and z, respectively, where the total of R32, HFO-1132(E) and R1234yf is (100-w) mass% in the composition diagram of 3 components,
when w is more than 0 and less than or equal to 1.2, the coordinates (x, y, z) are within the range of a graph formed by a curve IJ and a curve JK respectively connecting 5 points of the point I, the point J, the point K, the point F and the point C, and a straight line KF, a straight line FC and a straight line CI, or on the line segment, wherein the points on the straight line CI are not included,
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Points F (-0.0833 w +36.717, -4.0833 w +5.1833,3.1666w +58.0997),
Point C (0.0, -4.9167 w +58.317,3.9167w + 41.683);
when w is more than 1.2 and less than or equal to 1.3, the coordinates (x, y, z) are within the range of a graph formed by a curve IJ and a curve JK respectively connecting 5 points of the point I, the point J, the point K, the point F and the point C, and a straight line KF, a straight line FC and a straight line CI, or on the line segment, wherein points on the straight line CI are not included,
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point F (36.6, -3 w +3.9,2w +59.5),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w+41.553)；
When w is more than 1.3 and less than or equal to 4.0, the coordinates (x, y, z) are in the range of a graph formed by 6 points of a point I, a point J, a point K, a point B ', a point D and a point C, a curve IJ and a curve JK, a straight line KB ', a straight line B ' D, a straight line DC and a straight line CI or on the line segment, wherein the points on the straight line CI are not included,
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point B' (36.6,0.0, -w +63.4),
Point D (-2.8226 w +40.211,0.0,1.8226w +59.789),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w+41.553)；
When w is more than 4.0 and less than or equal to 7.0, the coordinates (x, y, z) are in the range of a graph formed by 6 points of the point I, the point J, the point K, the point B ', the point D and the point C, the curve IJ and the curve JK, the straight line KB ', the straight line B ' D, the straight line DC and the straight line CI or on the line segment, wherein the points on the straight line CI are not included,
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point B' (36.6,0.0, -w +63.4),
Point D (-2.8 w +40.1,0.0,1.8w +59.9),
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w+41.7)，
And the number of the first and second electrodes,
curve IJ is represented by coordinates (x,0.0236 x)2－1.716x+72,－0.0236x2+0.716x + 28-w) represents,
curve JK consists of coordinates (x,0.0095 x)2－1.2222x+67.676,－0.0095x2+0.2222x + 32.324-w).
3. A refrigerant-containing composition characterized by:
the refrigerant contains CO2And R32, HFO-1132(E) and R1234yf, to convert CO2And R32, HFO-1132(E) and R1234yf are w and x, y and z, respectively, where the total of R32, HFO-1132(E) and R1234yf is (100-w) mass% in the composition diagram of 3 components,
when w is more than 0 and less than or equal to 1.2, the coordinates (x, y, z) are in the range of a graph formed by a curve IJ and a curve JK respectively connecting 4 points of the point I, the point J, the point E and the point C, a straight line KF, a straight line FC and a straight line CI, or on the line segment, wherein the points on the straight line CI are not included,
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point E (18.2, -1.1111 w)2－3.1667w+31.9,1.1111w2+2.1667w+49.9)、
Point C (0.0, -4.9167 w +58.317,3.9167w + 41.683);
when w is more than 1.2 and less than or equal to 4.0, the coordinate (x, y, z) is in the range of a graph formed by a curve IJ and a curve JK respectively connecting 4 points of the point I, the point J, the point E and the point C, and a straight line KF, a straight line FC and a straight line CI or on the line segment, wherein the points on the straight line CI are not included,
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point E (-0.0365 w +18.26,0.0623 w)2－4.5381w+31.856,－0.0623w2+3.5746w+49.884)、
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w+41.553)；
When w is more than 4.0 and less than or equal to 7.0, the coordinates (x, y, z) are within the range of a graph formed by a curve IJ and a curve JK respectively connecting 4 points of the point I, the point J, the point E and the point C, and a straight line KF, a straight line FC and a straight line CI, or on the line segment, wherein points on the straight line CI are not included,
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point E (18.1,0.0444 w)2－4.3556w+31.411,－0.0444w2+3.3556w+50.489)、
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w+41.7)；
And the number of the first and second electrodes,
curve IJ is represented by coordinates (x,0.0236 x)2－1.716x+72,－0.0236x2+0.716x + 28-w).
4. A refrigerant-containing composition characterized by:
the refrigerant contains CO2And R32, HFO-1132(E) and R1234yf, to convert CO2And R32, HFO-1132(E) and R1234yf are w and x, y and z, respectively, where the total of R32, HFO-1132(E) and R1234yf is (100-w) mass% in the composition diagram of 3 components,
when w is more than 0 and less than or equal to 0.6, the coordinates (x, y, z) are within the range of a graph formed by a curve GO and a curve OP which respectively connect 5 points of the point G, the point O, the point P, the point B and the point D, and a straight line PB ', a straight line B ' D and a straight line DG, or on the line segment, wherein the points on the straight line B ' D are not included,
point G (-5.8333 w)2－3.1667w+22.2,7.0833w2+1.4167w+26.2,－1.25w2+0.75w+51.6)、
Point O (36.8,0.8333 w)2+1.8333w+22.6,－0.8333w2－2.8333w+40.6)、
Point P (51.7,1.1111 w)2+20.5,－1.1111w2－w+27.8)、
Point B "(-1.5278 w)2+2.75w+50.5,0.0,1.5278w2－3.75w+49.5)、
Point D (-2.9167 w +40.317,0.0,1.9167w + 59.683);
when w is more than 0.6 and less than or equal to 1.2, the coordinates (x, y, z) are within the range of a graph formed by a curve GN, a curve NO and a curve OP, and a straight line PB ', a straight line B' D and a straight line DG respectively connecting 6 points of the points G, N, O, P, B ', D or the line segment excluding the points on the straight line B' D,
point G (-5.8333 w)2－3.1667w+22.2,7.0833w2+1.4167w+26.2,－1.25w2+0.75w+51.6)、
Point N (18.2,0.2778w2+3w +27.7, -0.2778 w 2-4 w +54.1),
Point O (36.8,0.8333 w)2+1.8333w+22.6,－0.8333w2－2.8333w+40.6)、
Point P (51.7,1.1111 w)2+20.5,－1.1111w2－w+27.8)、
Point B "(-1.5278 w)2+2.75w+50.5,0.0,1.5278w2－3.75w+49.5)、
Point D (-2.9167 w +40.317,0.0,1.9167w + 59.683);
and the number of the first and second electrodes,
the curve GO is represented by the coordinates (x, (0.00487 w) when w is more than 0 and less than or equal to 0.62－0.0059w+0.0072)x2+(－0.279w2+0.2844w－0.6701)x+3.7639w2-0.2467 w +37.512,100-w-x-y),
the curve GN is represented by the coordinates (x, (0.0122 w) when w is more than 0.6 and less than or equal to 1.22－0.0113w+0.0313)x2+(－0.3582w2+0.1624w－1.4551)x+2.7889w2+3.7417w +43.824,100-w-x-y),
the curve NO is represented by the coordinates (x, (0.00487 w) when w is more than 0.6 and less than or equal to 1.22－0.0059w+0.0072)x2+(－0.279w2+0.2844w－0.6701)x+3.7639w2-0.2467 w +37.512,100-w-x-y),
when the curve OP is more than 0 and less than or equal to 1.2, the curve consists of coordinates (x, (0.0074 w)2－0.0133w+0.0064)x2+(－0.5839w2+1.0268w－0.7103)x+11.472w2-17.455 w +40.07,100-w-x-y),
when W is more than 1.2 and less than or equal to 4.0, the coordinates (x, y, z) are within the range of a graph formed by 8 points of a curve MW, a curve WN, a curve NO, a curve OP, a straight line PB ', a straight line B' D, a straight line DC and a straight line CM, or on the line segment, which respectively connect the points M, W, N, O, P, B ', D and C, wherein the points B' D and the straight line CM are not included,
point M (0.0, -0.3004 w)2+2.419w+55.53,0.3004w2－3.419w+44.47)、
Point W (10.0, -0.3645W)2+3.5024w+34.422,0.3645w2－4.5024w+55.578)、
Point N (18.2, -0.3773 w)2+3.319w+28.26,0.3773w2－4.319w+53.54)、
Point O (36.8, -0.1392 w)2+1.4381w+24.475,0.1392w2－2.4381w+38.725)、
Point P (51.7, -0.2381 w)2+1.881w+20.186,0.2381w2－2.881w+28.114)、
Point B "(51.6,0.0, -w +48.4),
Point D (-2.8226 w +40.211,0.0,1.8226w +59.789),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w+41.553)；
And the number of the first and second electrodes,
the curve MW is represented by the coordinates (x, (0.0043 w)2－0.0359w+0.1509)x2+(－0.0493w2+0.4669w－3.6193)x－0.3004w2+2.419w +55.53,100-w-x-y),
the curve WN is represented by the coordinates (x, (0.0055 w)2－0.0326w+0.0665)x2+(－0.1571w2+0.8981w－2.6274)x+0.6555w2-2.2153 w +54.044,100-w-x-y),
curve NO consists of the coordinates (x, (-0.00062 w)2+0.0036w+0.0037)x2+(0.0375w2－0.239w－0.4977)x－0.8575w2+6.4941w +36.078,100-w-x-y),
the curve OP is composed of coordinates (x, (-0.000463 w)2+0.0024w－0.0011)x2+(0.0457w2－0.2581w－0.075)x－1.355w2+8.749w +27.096,100-w-x-y),
when W is more than 4.0 and less than or equal to 7.0, the coordinates (x, y, z) are within the range of a graph formed by 8 points of a curve MW, a curve WN, a curve NO, a curve OP, a straight line PB ', a straight line B' D, a straight line DC and a straight line CM, or on the line segment, which respectively connect the points M, W, N, O, P, B ', D, and C, excluding the points on the straight line B' D and the straight line CM,
point M (0.0, -0.0667 w)2+0.8333w+58.133,0.0667w2－1.8333w+41.867)、
Point W (10.0, -0.0667W)2+1.1w+39.267,0.0667w2－2.1w+50.733)、
Point N (18.2, -0.0889 w)2+1.3778w+31.411,0.0889w2－2.3778w+50.389)、
Point O (36.8, -0.0444 w)2+0.6889w+25.956,0.0444w2－1.6889w+37.244)、
Point P (51.7, -0.0667 w)2+0.8333w+21.633,0.0667w2－1.8333w+26.667)、
Point B "(51.6,0.0, -w +48.4),
Point D (-2.8 w +40.1,0.0,1.8w +59.9),
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w+41.7)；
And the number of the first and second electrodes,
the curve MW is represented by the coordinates (x, (0.00357 w)2－0.0391w+0.1756)x2+(－0.0356w2+0.4178w－3.6422)x－0.0667w2+0.8333w +58.103,100-w-x-y),
the curve WN is composed of coordinates (x, (-0.002061 w)2+0.0218w－0.0301)x2+(0.0556w2－0.5821w－0.1108)x－0.4158w2+4.7352w +43.383,100-w-x-y),
curve NO consists of the coordinates (x,0.0082 x)2+(0.0022w2－0.0345w－0.7521)x－0.1307w2+2.0247w +42.327,100-w-x-y),
the curve OP is composed of coordinates (x, (-0.0006258 w)2+0.0066w－0.0153)x2+(0.0516w2－0.5478w+0.9894)x－1.074w2+11.651w +10.992,100-w-x-y).
5. A refrigerant-containing composition characterized by:
the refrigerant contains CO2And R32, HFO-1132(E) and R1234yf, to convert CO2And R32, HFO-1132(E) and R1234yf are w and x, y and z, respectively, where the total of R32, HFO-1132(E) and R1234yf is (100-w) mass% in the composition diagram of 3 components,
when w is more than 0 and less than or equal to 0.6, the coordinate (x, y, z) is in the range OF a graph formed by a curve GO and a straight line OF which are respectively connected with 3 points OF a point G, a point O and a point F or on the line segment,
point G (-5.8333 w)2－3.1667w+22.2,7.0833w2+1.4167w+26.2,－1.25w2+0.75w+51.6)、
Point O (36.8,0.8333 w)2+1.8333w+22.6,－0.8333w2－2.8333w+40.6)、
Point F (-0.0833 w +36.717, -4.0833 w +5.1833,3.1666w + 58.0997);
and the number of the first and second electrodes,
curve GO consists of coordinates (x, (0.00487 w)2－0.0059w+0.0072)x2+(－0.279w2+0.2844w－0.6701)x+3.7639w2-0.2467 w +37.512,100-w-x-y),
when w is more than 0.6 and less than or equal to 1.2, the coordinates (x, y, z) are within the range OF a graph formed by a curve GN and a curve NO connecting 4 points OF the point G, the point N, the point O and the point F, and a straight line OF and a straight line FG, or on the line segment,
point G (-5.8333 w)2－3.1667w+22.2,7.0833w2+1.4167w+26.2,－1.25w2+0.75w+51.6)、
Point N (18.2,0.2778 w)2+3.0w+27.7,－0.2.778w2－4.0w+54.1)、
Point O (36.8,0.8333 w)2+1.8333w+22.6,－0.8333w2－2.8333w+40.6)、
Point F (-0.0833 w +36.717, -4.0833 w +5.1833,3.1666w + 58.0997);
and the number of the first and second electrodes,
the curve GN is represented by the coordinates (x, (0.0122 w) when w is more than 0.6 and less than or equal to 1.22－0.0113w+0.0313)x2+(－0.3582w2+0.1624w－1.4551)x+2.7889w2+3.7417w +43.824,100-w-x-y),
the curve NO is represented by the coordinates (x, (0.00487 w) when w is more than 0.6 and less than or equal to 1.22－0.0059w+0.0072)x2+(－0.279w2+0.2844w－0.6701)x+3.7639w2-0.2467 w +37.512,100-w-x-y),
when W is more than 1.2 and less than or equal to 1.3, the coordinates (x, y, z) are within the range OF a graph formed by a curve MW, a curve WN, a curve NO, a straight line OF, a straight line FC, and a straight line CM, or on the line segment, respectively connecting 6 points OF the points M, W, N, O, F, and C, excluding the points on the straight line CM,
point M (0.0, -0.3004 w)2+2.419w+55.53,0.3004w2－3.419w+44.47)、
Point W (10.0, -0.3645W)2+3.5024w+34.422,0.3645w2－4.5024w+55.578)、
Point N (18.2, -0.3773 w)2+3.319w+28.26,0.3773w2－4.319w+53.54)、
Point O (36.8, -0.1392 w)2+1.4381w+24.475,0.1392w2－2.4381w+38.725)、
Point F (36.6, -3 w +3.9,2w +59.5),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w+41.553)；
And the number of the first and second electrodes,
the curve MW is represented by the coordinates (x, (0.0043 w)2－0.0359w+0.1509)x2+(－0.0493w2+0.4669w－3.6193)x－0.3004w2+2.419w +55.53,100-w-x-y),
the curve WN is represented by the coordinates (x, (0.0055 w)2－0.0326w+0.0665)x2+(－0.1571w2+0.8981w－2.6274)x+0.6555w2-2.2153 w +54.044,100-w-x-y),
curve NO consists of the coordinates (x, (-0.00062 w)2+0.0036w+0.0037)x2+(0.0375w2－0.239w－0.4977)x－0.8575w2+6.4941w +36.078,100-w-x-y),
when W is more than 1.3 and less than or equal to 4.0, the coordinates (x, y, z) are within the range of a graph formed by a curve MW, a curve WN, a curve NO, a straight line OB ', a straight line B ' D, a straight line DC, and a straight line CM, or on the line segment, respectively connecting 7 points of the points M, W, N, O, B ', D, and C, excluding the points on the straight line CM,
point M (0.0, -0.3004 w)2+2.419w+55.53,0.3004w2－3.419w+44.47)、
Point W (10.0, -0.3645W)2+3.5024w+34.422,0.3645w2－4.5024w+55.578)、
Point N (18.2, -0.3773 w)2+3.319w+28.26,0.3773w2－4.319w+53.54)、
Point O (36.8, -0.1392 w)2+1.4381w+24.475,0.1392w2－2.4381w+38.725)、
Point B' (36.6,0.0, -w +63.4),
Point D (-2.8226 w +40.211,0.0,1.8226w +59.789),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w+41.553)；
And the number of the first and second electrodes,
the curve MW is represented by the coordinates (x, (0.0043 w)2－0.0359w+0.1509)x2+(－0.0493w2+0.4669w－3.6193)x－0.3004w2+2.419w +55.53,100-w-x-y),
the curve WN is represented by the coordinates (x, (0.0055 w)2－0.0326w+0.0665)x2+(－0.1571w2+0.8981w－2.6274)x+0.6555w2-2.2153 w +54.044,100-w-x-y),
curve NO consists of the coordinates (x, (-0.00062 w)2+0.0036w+0.0037)x2+(0.0375w2－0.239w－0.4977)x+(－0.8575w2+6.4941w +36.078), 100-w-x-y),
when W is more than 4.0 and less than or equal to 7.0, the coordinates (x, y, z) are within the range of a graph formed by a curve MW, a curve WN, a curve NO, a straight line OB ', a straight line B ' D, a straight line DC, and a straight line CM, or on the line segment, respectively connecting 7 points of the points M, W, N, O, B ', D, and C, excluding the points on the straight line CM,
point M (0.0, -0.0667 w)2+0.8333w+58.133,0.0667w2－1.8333w+41.867)、
Point W (10.0, -0.0667W)2+1.1w+39.267,0.0667w2－2.1w+50.733)、
Point N (18.2, -0.0889 w)2+1.3778w+31.411,0.0889w2－2.3778w+50.389)、
Point O (36.8, -0.0444 w)2+0.6889w+25.956,0.0444w2－1.6889w+37.244)、
Point B' (36.6,0.0, -w +63.4),
Point D (-2.8 w +40.1,0.0,1.8w +59.9),
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w+41.7)；
And the number of the first and second electrodes,
the curve MW is represented by the coordinates (x, (0.00357 w)2－0.0391w+0.1756)x2+(－0.0356w2+0.4178w－3.6422)x－0.0667w2+08333w +58.103,100-w-x-y),
the curve WN is composed of coordinates (x, (-0.002061 w)2+0.0218w－0.0301)x2+(0.0556w2－0.5821w－0.1108)x－0.4158w2+4.7352w +43.383,100-w-x-y),
curve NO consists of the coordinates (x, (0.0082 x)2+(0.0022w2－0.0345w－0.7521)x－0.1307w2+2.0247w +42.327,100-w-x-y).
6. A refrigerant-containing composition characterized by:
the refrigerant contains CO2And R32, HFO-1132(E) and R1234yf, to convert CO2And R32, HFO-1132(E) and R1234yf are w and x, y and z, respectively, where the total of R32, HFO-1132(E) and R1234yf is (100-w) mass% in the composition diagram of 3 components,
when W is more than 1.2 and less than or equal to 4.0, the coordinates (x, y, z) are within the range of a graph formed by a curve MW and a curve WN connecting 5 points of the points M, W, N, E and C, respectively, and a straight line NE, a straight line EC and a straight line CM, or on the line segment, excluding the points on the straight line CM,
point M (0.0, -0.3004 w)2+2.419w+55.53,0.3004w2－3.419w+44.47)、
Point W (10.0, -0.3645W)2+3.5024w+34.422,0.3645w2－4.5024w+55.578)、
Point N (18.2, -0.3773 w)2+3.319w+28.26,0.3773w2－4.319w+53.54)、
Point E (-0.0365 w +18.26,0.0623 w)2－4.5381w+31.856,－0.0623w2+3.5746w+49.884)、
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w+41.553)；
And the number of the first and second electrodes,
the curve MW is represented by the coordinates (x, (0.0043 w)2－0.0359w+0.1509)x2+(－0.0493w2+0.4669w－3.6193)x－0.3004w2+2.419w +55.53,100-w-x-y),
the curve WN is represented by the coordinates (x, (0.0055 w)2－0.0326w+0.0665)x2+(－0.1571w2+0.8981w－2.6274)x+0.6555w2-2.2153 w +54.044,100-w-x-y),
when W is greater than 4.0 and less than or equal to 7.0, the coordinates (x, y, z) are within the range of a graph formed by a curve MW and a curve WN connecting 5 points of the points M, W, N, E, and C, respectively, and a straight line NE, a straight line EC, and a straight line CM, or on the line segment, excluding the points on the straight line CM,
point M (0.0, -0.0667 w)2+0.8333w+58.133,0.0667w2－1.8333w+41.867)、
Point W (10.0, -0.0667W)2+1.1w+39.267,0.0667w2－2.1w+50.733)；
Point N (18.2, -0.0889 w)2+1.3778w+31.411,0.0889w2－2.3778w+50.389)、
Point E (18.1,0.0444 w)2－4.3556w+31.411,－0.0444w2+3.3556w+50.489)、
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w+41.7)；
And the number of the first and second electrodes,
the curve MW is represented by the coordinates (x, (0.00357 w)2－0.0391w+0.1756)x2+(－0.0356w2+0.4178w－3.6422)x－0.0667w2+0.8333w +58.103,100-w-x-y),
the curve WN is composed of coordinates (x, (-0.002061 w)2+0.0218w－0.0301)x2+(0.0556w2－0.5821w－0.1108)x－0.4158w2+4.7352w +43.383,100-w-x-y).
7. The composition of any one of claims 1 to 6, wherein:
also contains a refrigerator oil, and the composition is used as a working fluid for refrigerators.
8. The composition of any one of claims 1 to 7, wherein:
which is used as a replacement refrigerant for R410A.
9. Use of the composition of any one of claims 1 to 7 as a replacement refrigerant for R410A.
10. A freezer, characterized by:
a working fluid comprising the composition according to any one of claims 1 to 7.
11. A method for operating a refrigerator, comprising:
a process for using the composition according to any one of claims 1 to 7 as a working fluid and circulating the working fluid in a refrigerator.
Technical Field
The present invention relates to a refrigerant-containing composition, use thereof, a refrigerator having the same, and a method for operating the refrigerator.
Background
R410A is currently used as a refrigerant for air conditioning such as a household air conditioner. R410A is difluoromethane (CH)2F2(ii) a HFC-32 or R32) and pentafluoroethane (C)2HF5(ii) a HFC-125 or R125) is an azeotrope-like composition.
However, since the Global Warming Potential (GWP) of R410A is 2088 and there is a high concern about global warming, R32 having a GWP of 675 is used more often.
Therefore, various low GWP mixed refrigerants capable of replacing R410A have been proposed (patent document 1).
Documents of the prior art
Patent document
Patent document 1: international publication No. 2015/186557
Disclosure of Invention
Technical problem to be solved by the invention
The inventors of the present invention have found, through their own studies, that there has not been developed a refrigerant composition having three performances of a Refrigeration Capacity (sometimes referred to as a Cooling Capacity or a Capacity) equivalent to R410A and a GWP sufficiently low and a low combustibility (class 2L) according to the american society for heating, Refrigeration and air conditioning (ASHRAE) standard. The present invention aims to solve such a unique technical problem.
Technical solution for solving technical problem
Item 1A refrigerant composition comprising CO as a refrigerant2And trans-1, 2-difluoroethylene (HFO-1132(E)), difluoromethane (R32) and 2,3,3, 3-tetrafluoro-1-propene (R1234yf), and reacting CO2And R32, HFO-1132(E) and R1234yf are w and x, y and z, respectively, where the total of R32, HFO-1132(E) and R1234yf is (100-w) mass% in the composition diagram of 3 components,
when w is more than 0 and less than or equal to 1.2, the coordinates (x, y, z) are within the range of a graph formed by connecting 7 points of the point I, the point J, the point K, the point L, the point B ', the point D and the point C, the curve IJ, the curve JK, the curve KL, the line LB', the line B ', the line DC and the line CI, or on the line segment (wherein, the points on the line B' D and the line CI are not included),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point L (51.7,28.9, 19.4-w),
Point B "(-1.5278 w)2+2.75w+50.5,0.0,1.5278w2－3.75w+49.5)、
Point D (-2.9167 w +40.317,0.0,1.9167w +59.683),
Point C (0.0, -4.9167 w +58.317,3.9167w +41.683),
when w is more than 1.2 and less than or equal to 4.0, the coordinates (x, y, z) are within the range of a graph formed by connecting 7 points of the point I, the point J, the point K, the point L, the point B, the point D and the point C, the curve JJ, the curve JK, the curve KL, the line LB, the line B 'D, the line DC and the line CI, or on the line segment (wherein, the points on the line B' D and the line CI are not included),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point L (51.7,28.9, 19.4-w),
Point B "(51.6,0.0, 48.4-w),
Point D (-2.8226 w +40.211,0.0,1.8226w +59.789),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w+41.553)，
When w is more than 4.0 and less than or equal to 7.0, the coordinates (x, y, z) are within the range of a graph formed by connecting 7 points of the point I, the point J, the point K, the point L, the point B ', the point D and the point C, the curve JJ, the curve JK, the curve KL, the line LB', the line B ', the line DC and the line CI, or on the line segment (wherein, the points on the line B', the line D and the line CI are not included),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point L (51.7,28.9, 19.4-w),
Point B "(51.6,0.0, 48.4-w),
Point D (-2.8 w +40.1,0.0,1.8w +59.9),
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w +41.7), and,
curve IJ is represented by coordinates (x,0.0236 x)2－1.716x+72,－0.0236x2+0.716x + 28-w) represents,
curve JK consists of coordinates (x,0.0095 x)2－1.2222x+67.676,－0.0095x2+0.2222x + 32.324-w),
the curve KL is represented by the coordinates (x,0.0049 x)2－0.8842x+61.488,－0.0049x2-0.1158 x + 38.512-w).
Item 2. a composition comprising a refrigerant, wherein the refrigerant comprises CO2And trans-1, 2-difluoroethylene (HFO-1132(E)), difluoromethane (R32) and 2,3,3, 3-tetrafluoro-1-propene (R1234yf), and reacting CO2And R32, HFO-1132(E) and R1234yf are w and x, y and z, respectively, where the total of R32, HFO-1132(E) and R1234yf is (100-w) mass% in the composition diagram of 3 components,
when w is more than 0 and less than or equal to 1.2, the coordinates (x, y, z) are within the range of a graph formed by a curve IJ and a curve JK connecting 5 points of the point I, the point J, the point K, the point F and the point C, and a straight line KF, a straight line FC and a straight line CI or on the line segment (wherein, the points on the straight line CI are not included),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Points F (-0.0833 w +36.717, -4.0833 w +5.1833,3.1666w +58.0997),
Point C (0.0, -4.9167 w +58.317,3.9167w +41.683),
when w is more than 1.2 and less than or equal to 1.3, the coordinates (x, y, z) are within the range of a graph formed by a curve IJ and a curve JK connecting 5 points of the point I, the point J, the point K, the point F and the point C, a straight line KF, a straight line FC and a straight line CI, or on the line segment (excluding the point on the straight line CI),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point F (36.6, -3 w +3.9,2w +59.5),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w+41.553)，
When w is more than 1.3 and less than or equal to 4.0, the coordinates (x, y, z) are within the range of the graph formed by 6 points of the point I, the point J, the point K, the point B ', the point D and the point C, the curve IJ and the curve JK, the straight line KB ', the straight line B ' D, the straight line DC and the straight line CI or on the line segment (wherein, the points on the straight line CI are not included),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point B' (36.6,0.0, -w +63.4),
Point D (-2.8226 w +40.211,0.0,1.8226w +59.789),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w+41.553)，
When w is more than 4.0 and less than or equal to 7.0, the coordinates (x, y, z) are within the range of the graph formed by 6 points including the point I, the point J, the point K, the point B ', the point D and the point C, the curve IJ and the curve JK, the straight line KB ', the straight line B ' D, the straight line DC and the straight line CI or on the line segment (wherein, the points on the straight line CI are not included),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point B' (36.6,0.0, -w +63.4),
Point D (-2.8 w +40.1,0.0,1.8w +59.9),
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w +41.7), and,
curve IJ is represented by coordinates (x,0.0236 x)2－1.716x+72,－0.0236x2+0.716x + 28-w) represents,
curve JK consists of coordinates (x,0.0095 x)2－1.2222x+67.676,－0.0095x2+0.2222x + 32.324-w).
Item 3. a composition comprising a refrigerant, wherein the refrigerant comprises CO2And R32, HFO-1132(E) and R1234yf, to convert CO2And R32, HFO-1132(E) and R1234yf are w and x, y and z, respectively, where the total of R32, HFO-1132(E) and R1234yf is (100-w) mass% in the composition diagram of 3 components,
when w is more than 0 and less than or equal to 1.2, the coordinates (x, y, z) are within the range of a graph formed by a curve IJ and a curve JK respectively connecting 4 points of the point I, the point J, the point E and the point C and a straight line KF, a straight line FC and a straight line CI or on the line segment (wherein, the points on the straight line CI are not included),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point E (18.2, -1.1111 w)2－3.1667w+31.9,1.1111w2+2.1667w+49.9)、
Point C (0.0, -4.9167 w +58.317,3.9167w +41.683),
when w is more than 1.2 and less than or equal to 4.0, the coordinates (x, y, z) are within the range of a graph formed by a curve IJ and a curve JK connecting 4 points of the point I, the point J, the point E and the point C, respectively, and a straight line KF, a straight line FC and a straight line CI, or on the line segment (excluding the points on the straight line CI),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point E (-0.0365 w +18.26,0.0623 w)2－4.5381w+31.856,－0.0623w2+3.5746w+49.884)、
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w+41.553)，
When w is more than 4.0 and less than or equal to 7.0, the coordinates (x, y, z) are within the range of a graph formed by a curve IJ and a curve JK connecting 4 points of the point I, the point J, the point E, and the point C, respectively, and a straight line KF, a straight line FC, and a straight line CI, or on the line segment (excluding the points on the straight line CI),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point E (18.1,0.0444 w)2－4.3556w+31.411,－0.0444w2+3.3556w+50.489)、
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w +41.7), and,
curve IJ is represented by coordinates (x,0.0236 x)2－1.716x+72,－0.0236x2+0.716x + 28-w).
Item 4. a composition comprising a refrigerant, wherein the refrigerant comprises CO2And R32, HFO-1132(E) and R1234yf, to convert CO2And R32, HFO-1132(E) and R1234yf are w and x, y and z, respectively, where the total of R32, HFO-1132(E) and R1234yf is (100-w) mass% in the composition diagram of 3 components,
when w is more than 0 and less than or equal to 0.6, the coordinates (x, y, z) are within the range of a graph formed by a curve GO and a curve OP, a straight line PB ', a straight line B' D and a straight line DG respectively connecting 5 points of the point G, the point O, the point P and the point B ', and the point D, or on the line segment (excluding the point on the straight line B' D),
point G (-5.8333 w)2－3.1667w+22.2,7.0833w2+1.4167w+26.2,－1.25w2+0.75w+51.6)、
Point O (36.8,0.8333 w)2+1.8333w+22.6,－0.8333w2－2.8333w+40.6)、
Point P (51.7,1.1111 w)2+20.5,－1.1111w2－w+27.8)、
Point B "(-1.5278 w)2+2.75w+50.5,0.0,1.5278w2-3.75 w +49.5), point D (-2.9167 w +40.317,0.0,1.9167w +59.683),
when w is more than 0.6 and less than or equal to 1.2, the coordinates (x, y, z) are within the range of a figure formed by a curve GN, a curve NO, a curve OP, a straight line PB ', a straight line B' D and a straight line DG respectively connecting 6 points of the points G, N, O, P, B ', D or the line segment (excluding the points on the straight line B' D),
point G (-5.8333 w)2－3.1667w+22.2,7.0833w2+1.4167w+26.2,－1.25w2+0.75w+51.6)、
Point N (18.2,0.2778 w)2+3w+27.7,－0.2778w2－4w+54.1)、
Point O (36.8,0.8333 w)2+1.8333w+22.6,－0.8333w2－2.8333w+40.6)、
Point P (51.7,1.1111 w)2+20.5,－1.1111w2－w+27.8)、
Point B "(-1.5278 w)2+2.75w+50.5,0.0,1.5278w2-3.75 w +49.5), point D (-2.9167 w +40.317,0.0,1.9167w +59.683), and,
the curve GO is represented by the coordinates (x, (0.00487 w) when w is more than 0 and less than or equal to 0.62－0.0059w+0.0072)x2+(－0.279w2+0.2844w－0.6701)x+3.7639w2-0.2467 w +37.512,100-w-x-y),
the curve GN is represented by the coordinates (x, (0.0122 w) when w is more than 0.6 and less than or equal to 1.22－0.0113w+0.0313)x2+(－0.3582w2+0.1624w－1.4551)x+2.7889w2+3.7417w +43.824,100-w-x-y),
the curve NO is represented by the coordinates (x, (0.00487 w) when w is more than 0.6 and less than or equal to 1.22－0.0059w+0.0072)x2+(－0.279w2+0.2844w－0.6701)x+3.7639w2-0.2467 w +37.512,100-w-x-y),
when the curve OP is more than 0 and less than or equal to 1.2, the curve consists of coordinates (x, (0.0074 w)2－0.0133w+0.0064)x2+(－0.5839w2+1.0268w－0.7103)x+11.472w2-17.455 w +40.07,100-w-x-y),
when W is more than 1.2 and less than or equal to 4.0, the coordinates (x, y, z) are within the range of a graph formed by 8 points of the points M, W, N, O, P, B, D and C, the curves WN, NO and OP, the lines PB, B ', D, DC and CM, or on the line segment (excluding the points on the lines B', D and CM),
point M (0.0, -0.3004 w)2+2.419w+55.53,0.3004w2－3.419w+44.47)、
Point W (10.0, -0.3645W)2+3.5024w+34.422,0.3645w2－4.5024w+55.578)、
Point N (18.2, -0.3773 w)2+3.319w+28.26,0.3773w2－4.319w+53.54)、
Point O (36.8, -0.1392 w)2+1.4381w+24.475,0.1392w2－2.4381w+38.725)、
Point P (51.7, -0.2381 w)2+1.881w+20.186,0.2381w2－2.881w+28.114)、
Point B "(51.6,0.0, -w +48.4),
Point D (-2.8226 w +40.211,0.0,1.8226w +59.789),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w +41.553), and,
the curve MW is represented by the coordinates (x, (0.0043 w)2－0.0359w+0.1509)x2+(－0.0493w2+0.4669w－3.6193)x－0.3004w2+2.419w +55.53,100-w-x-y),
the curve WN is represented by the coordinates (x, (0.0055 w)2－0.0326w+0.0665)x2+(－0.1571w2+0.8981w－2.6274)x+0.6555w2-2.2153 w +54.044,100-w-x-y),
curve NO consists of the coordinates (x, (-0.00062 w)2+0.0036w+0.0037)x2+(0.0375w2－0.239w－0.4977)x－0.8575w2+6.4941w +36.078,100-w-x-y),
curve OP byCoordinates (x, (-0.000463 w)2+0.0024w－0.0011)x2+(0.0457w2－0.2581w－0.075)x－1.355w2+8.749w +27.096,100-w-x-y),
when W is greater than 4.0 and less than or equal to 7.0, the coordinates (x, y, z) are within the range of a graph formed by 8 points, i.e., a curve MW, a curve WN, a curve NO, a curve OP, a straight line PB ', a straight line B' D, a straight line DC, and a straight line CM, connecting the points M, W, N, O, P, B ', D, and C, or on the line segment (excluding the points on the straight line B' D and the straight line CM),
point M (0.0, -0.0667 w)2+0.8333w+58.133,0.0667w2－1.8333w+41.867)、
Point W (10.0, -0.0667W)2+1.1w+39.267,0.0667w2－2.1w+50.733)、
Point N (18.2, -0.0889 w)2+1.3778w+31.411,0.0889w2－2.3778w+50.389)、
Point O (36.8, -0.0444 w)2+0.6889w+25.956,0.0444w2－1.6889w+37.244)、
Point P (51.7, -0.0667 w)2+0.8333w+21.633,0.0667w2－1.8333w+26.667)、
Point B "(51.6,0.0, -w +48.4),
Point D (-2.8 w +40.1,0.0,1.8w +59.9),
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w +41.7), and,
the curve MW is represented by the coordinates (x, (0.00357 w)2－0.0391w+0.1756)x2+(－0.0356w2+0.4178w－3.6422)x－0.0667w2+0.8333w +58.103,100-w-x-y),
the curve WN is composed of coordinates (x, (-0.002061 w)2+0.0218w－0.0301)x2+(0.0556w2－0.5821w－0.1108)x－0.4158w2+4.7352w +43.383,100-w-x-y),
curve NO consists of the coordinates (x,0.0082 x)2+(0.0022w2－0.0345w－0.7521)x－0.1307w2+2.0247w +42.327,100-w-x-y),
CurveOP is composed of coordinates (x, (-0.0006258 w)2+0.0066w－0.0153)x2+(0.0516w2－0.5478w+0.9894)x－1.074w2+11.651w +10.992,100-w-x-y).
Item 5. A composition comprising a refrigerant, wherein the refrigerant comprises CO2And R32, HFO-1132(E) and R1234yf, to convert CO2And R32, HFO-1132(E) and R1234yf are w and x, y and z, respectively, where the total of R32, HFO-1132(E) and R1234yf is (100-w) mass% in the composition diagram of 3 components,
when w is more than 0 and less than or equal to 0.6, the coordinate (x, y, z) is within the range OF a graph formed by a curve GO and a straight line OF and a straight line FG respectively connecting 3 points OF a point G, a point O and a point F or on the line segment,
point G (-5.8333 w)2－3.1667w+22.2,7.0833w2+1.4167w+26.2,－1.25w2+0.75w+51.6)、
Point O (36.8,0.8333 w)2+1.8333w+22.6,－0.8333w2－2.8333w+40.6)、
Point F (-0.0833 w +36.717, -4.0833 w +5.1833,3.1666w +58.0997), and,
curve GO consists of coordinates (x, (0.00487 w)2－0.0059w+0.0072)x2+(－0.279w2+0.2844w－0.6701)x+3.7639w2-0.2467 w +37.512,100-w-x-y),
when w is more than 0.6 and less than or equal to 1.2, the coordinates (x, y, z) are within the range OF a graph formed by a curve GN and a curve NO and a straight line OF and a straight line FG respectively connecting 4 points OF the point G, the point N, the point O and the point F or on the line segment,
point G (-5.8333 w)2－3.1667w+22.2,7.0833w2+1.4167w+26.2,－1.25w2+0.75w+51.6)、
Point N (18.2,0.2778 w)2+3.0w+27.7,－0.2.778w2－4.0w+54.1)、
Point O (36.8,0.8333 w)2+1.8333w+22.6,－0.8333w2－2.8333w+40.6)、
Point F (-0.0833 w +36.717, -4.0833 w +5.1833,3.1666w +58.0997), and,
the curve GN is represented by the coordinates (x, (0.0122 w) when w is more than 0.6 and less than or equal to 1.22－0.0113w+0.0313)x2+(－0.3582w2+0.1624w－1.4551)x+2.7889w2+3.7417w +43.824,100-w-x-y),
the curve NO is represented by the coordinates (x, (0.00487 w) when w is more than 0.6 and less than or equal to 1.22－0.0059w+0.0072)x2+(－0.279w2+0.2844w－0.6701)x+3.7639w2-0.2467 w +37.512,100-w-x-y),
when W is 1.2 < w.ltoreq.1.3, the coordinates (x, y, z) are within the range OF a graph formed by a curve MW, a curve WN, a curve NO, a straight line OF, a straight line FC, and a straight line CM, or on the line segment (excluding the points on the straight line CM), respectively connecting 6 points OF the points M, W, N, O, F, and C,
point M (0.0, -0.3004 w)2+2.419w+55.53,0.3004w2－3.419w+44.47)、
Point W (10.0, -0.3645W)2+3.5024w+34.422,0.3645w2－4.5024w+55.578)、
Point N (18.2, -0.3773 w)2+3.319w+28.26,0.3773w2－4.319w+53.54)、
Point O (36.8, -0.1392 w)2+1.4381w+24.475,0.1392w2－2.4381w+38.725)、
Point F (36.6, -3 w +3.9,2w +59.5),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w +41.553), and,
the curve MW is represented by the coordinates (x, (0.0043 w)2－0.0359w+0.1509)x2+(－0.0493w2+0.4669w－3.6193)x－0.3004w2+2.419w +55.53,100-w-x-y),
the curve WN is represented by the coordinates (x, (0.0055 w)2－0.0326w+0.0665)x2+(－0.1571w2+0.8981w－2.6274)x+0.6555w2-2.2153 w +54.044,100-w-x-y),
curve NO consists of the coordinates (x, (-0.00062 w)2+0.0036w+0.0037)x2+(0.0375w2－0.239w－0.4977)x－0.8575w2+6.4941w +36.078,100-w-x-y),
when W is more than 1.3 and less than or equal to 4.0, the coordinates (x, y, z) are within the range of a graph formed by 7 points of the points M, W, N, O, B ', D, C, the curves MW, WN, NO, OB ', B ', DC, and CM or on the line segment (excluding the points on CM),
point M (0.0, -0.3004 w)2+2.419w+55.53,0.3004w2－3.419w+44.47)、
Point W (10.0, -0.3645W)2+3.5024w+34.422,0.3645w2－4.5024w+55.578)、
Point N (18.2, -0.3773 w)2+3.319w+28.26,0.3773w2－4.319w+53.54)、
Point O (36.8, -0.1392 w)2+1.4381w+24.475,0.1392w2－2.4381w+38.725)、
Point B' (36.6,0.0, -w +63.4),
Point D (-2.8226 w +40.211,0.0,1.8226w +59.789),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w +41.553), and,
the curve MW is represented by the coordinates (x, (0.0043 w)2－0.0359w+0.1509)x2+(－0.0493w2+0.4669w－3.6193)x－0.3004w2+2.419w +55.53,100-w-x-y),
the curve WN is represented by the coordinates (x, (0.0055 w)2－0.0326w+0.0665)x2+(－0.1571w2+0.8981w－2.6274)x+0.6555w2-2.2153 w +54.044,100-w-x-y),
curve NO consists of the coordinates (x, (-0.00062 w)2+0.0036w+0.0037)x2+(0.0375w2－0.239w－0.4977)x+(－0.8575w2+6.4941w +36.078), 100-w-x-y),
when W is greater than 4.0 and less than or equal to 7.0, the coordinates (x, y, z) are within the range of a graph formed by a curve MW, a curve WN, a curve NO, a straight line OB ', a straight line B ' D, a straight line DC, and a straight line CM, which respectively connect 7 points of the points M, W, N, O, B ', D, and C, or on the line segment (excluding the points on the straight line CM),
point M (0.0, -0.0667 w)2+0.8333w+58.133,0.0667w2－1.8333w+41.867)、
Point W (10.0, -0.0667W)2+1.1w+39.267,0.0667w2－2.1w+50.733)、
Point N (18.2, -0.0889 w)2+1.3778w+31.411,0.0889w2－2.3778w+50.389)、
Point O (36.8, -0.0444 w)2+0.6889w+25.956,0.0444w2－1.6889w+37.244)、
Point B' (36.6,0.0, -w +63.4),
Point D (-2.8 w +40.1,0.0,1.8w +59.9),
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w +41.7), and,
the curve MW is represented by the coordinates (x, (0.00357 w)2－0.0391w+0.1756)x2+(－0.0356w2+0.4178w－3.6422)x－0.0667w2+0.8333w +58.103,100-w-x-y),
the curve WN is composed of coordinates (x, (-0.002061 w)2+0.0218w－0.0301)x2+(0.0556w2－0.5821w－0.1108)x－0.4158w2+4.7352w +43.383,100-w-x-y),
curve NO consists of the coordinates (x, (0.0082 x)2+(0.0022w2－0.0345w－0.7521)x－0.1307w2+2.0247w +42.327,100-w-x-y).
Item 6. a composition comprising a refrigerant, wherein the refrigerant comprises CO2And R32, HFO-1132(E) and R1234yf, to convert CO2And R32, HFO-1132(E) and R1234yf are w and x, y and z, respectively, where the total of R32, HFO-1132(E) and R1234yf is (100-w) mass% in the composition diagram of 3 components,
when W is more than 1.2 and less than or equal to 4.0, the coordinates (x, y, z) are within the range of a graph formed by a curve MW and a curve WN connecting 5 points of the points M, W, N, E, and C, respectively, and a straight line NE, a straight line EC, and a straight line CM, or on the line segment (excluding the points on the straight line CM),
point M (0.0, -0.3004 w)2+2.419w+55.53,0.3004w2－3.419w+44.47)、
Point W (10.0, -0.3645W)2+3.5024w+34.422,0.3645w2－4.5024w+55.578)、
Point N (18.2, -0.3773 w)2+3.319w+28.26,0.3773w2－4.319w+53.54)、
Point E (-0.0365 w +18.26,0.0623 w)2－4.5381w+31.856,－0.0623w2+3.5746w+49.884)、
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w +41.553), and,
the curve MW is represented by the coordinates (x, (0.0043 w)2－0.0359w+0.1509)x2+(－0.0493w 2+0.4669w－3.6193)x－0.3004w2+2.419w +55.53,100-w-x-y),
the curve WN is represented by the coordinates (x, (0.0055 w)2－0.0326w+0.0665)x2+(－0.1571w2+0.8981w－2.6274)x+0.6555w2-2.2153 w +54.044,100-w-x-y),
when W is greater than 4.0 and less than or equal to 7.0, the coordinates (x, y, z) are within the range of a graph formed by a curve MW and a curve WN connecting 5 points of the points M, W, N, E, and C, respectively, and a straight line NE, a straight line EC, and a straight line CM, or on the line segment (excluding the points on the straight line CM),
point M (0.0, -0.0667 w)2+0.8333w+58.133,0.0667w2－1.8333w+41.867)、
Point W (10.0, -0.0667W)2+1.1w+39.267,0.0667w2－2.1w+50.733)、
Point N (18.2, -0.0889 w)2+1.3778w+31.411,0.0889w2－2.3778w+50.389)、
Point E (18.1,0.0444 w)2－4.3556w+31.411,－0.0444w2+3.3556w+50.489)、
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w +41.7), and,
the curve MW is represented by the coordinates (x, (0.00357 w)2－0.0391w+0.1756)x2+(－0.0356w2+0.4178w－3.6422)x－0.0667w2+0.8333w +58.103,100-w-x-y),
the curve WN is composed of coordinates (x, (-0.002061 w)2+0.0218w－0.0301)x2+(0.0556w2－0.5821w－0.1108)x－0.4158w2+4.7352w +43.383,100-w-x-y).
The composition according to any one of items 1 to 6, which further contains a refrigerator oil, and the composition is used as a working fluid for refrigerators.
Item 8 the composition of any one of items 1 to 7, which is used as a substitute refrigerant for R410A.
The use of the composition of any one of items 1 to 7 as a refrigerant substitute for R410A.
A refrigerator according to item 10, which contains the composition according to any one of items 1 to 7 as a working fluid.
An operating method of a refrigerator, comprising a step of circulating the composition according to any one of items 1 to 7 in a refrigerator as a working fluid.
Effects of the invention
The refrigerant of the present invention has three properties of a cooling capacity equivalent to that of R410A, a sufficiently low GWP, and a low combustibility (2L class) according to the ASHRAE standard.
Drawings
FIG. 1 is a schematic view of an apparatus for measuring a combustion rate.
FIG. 2 is a view showing points and lines defining the refrigerant of the present invention in a composition diagram of 3 components in which the total of R32, HFO-1132(E) and R1234yf is 100 mass%.
FIG. 3 shows that the total of R32, HFO-1132(E) and R1234yf is 99.4% by mass (CO)2The content ratio is 0.6 mass%), and points and lines of the refrigerant of the present invention are defined in the composition diagram of 3 components.
FIG. 4 shows that the total of R32, HFO-1132(E) and R1234yf is 98.8 mass% (CO)2The content ratio is 1.2 mass%) of the 3-component composition diagram defines points and lines of the refrigerant of the present invention.
FIG. 5 shows that the total of R32, HFO-1132(E) and R1234yf is 98.7% by mass (CO)2The content ratio is 1.3 mass%) of the 3-component composition diagram defines points and lines of the refrigerant of the present invention.
FIG. 6 shows that the total of R32, HFO-1132(E) and R1234yf is 97.5% by mass (CO)2The content ratio is 2.5 mass%), and points and lines of the refrigerant of the present invention are defined in the composition diagram of 3 components.
FIG. 7 shows that the total of R32, HFO-1132(E) and R1234yf is 96% by mass (CO)2Content ratio of 4 mass%) of the refrigerant according to the present invention.
FIG. 8 shows that the total of R32, HFO-1132(E) and R1234yf is 94.5% by mass (CO)2The content ratio is 5.5 mass%), and points and lines of the refrigerant of the present invention are defined in the composition diagram of 3 components.
FIG. 9 shows that the total of R32, HFO-1132(E) and R1234yf is 93% by mass (CO)2The content ratio is 7 mass%) of the 3-component composition diagram defines points and lines of the refrigerant of the present invention.
Detailed Description
As a result of intensive studies by the inventors of the present invention to solve the above-mentioned problems, it was found that the composition contains CO2And R32, HFO-1132(E) and R1234yf have the above characteristics.
The present invention has been completed based on such findings. The present invention includes the following embodiments.
< definition of term >
In the present specification, the term "refrigerant" includes at least a compound specified by ISO817 (international standardization organization) and labeled with a refrigerant number (ASHRAE number) beginning with R indicating the kind of refrigerant, and also includes a compound having characteristics as a refrigerant equivalent to those of the above without labeling the refrigerant number. In view of the structure of the compound, refrigerants are roughly classified into "fluorocarbon-based compounds" and "non-fluorocarbon-based compounds". "fluorocarbon-based compounds" include chlorofluorocarbons (CFCs), Hydrochlorofluorocarbons (HCFCs), and Hydrofluorocarbons (HFCs). Examples of the "non-fluorocarbon compound" include propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744), and ammonia (R717).
In the present specification, the term "refrigerant-containing composition" comprises at least: (1) the refrigerant itself (including mixtures of refrigerants); (2) a composition which contains other components and can be used for obtaining a working fluid for a refrigerator by mixing at least refrigerator oil; (3) a working fluid for a refrigerator contains a refrigerator oil. In the present specification, the composition of (2) is distinguished from the refrigerant itself (including a mixture of refrigerants) and is labeled as a "refrigerant composition" in the three modes. The working fluid for a refrigerator in (3) is distinguished from the "refrigerant composition" and is labeled as "working fluid containing refrigerator oil".
In the present specification, the term "substitute" means that, when used in the context of "substituting" a first refrigerant with a second refrigerant, in a first type of equipment designed to operate using the first refrigerant, operation can be performed under optimum conditions using the second refrigerant only through modification of minute components (at least one of a refrigerator oil, a gasket, a packing, an expansion valve, a dryer, and other components) and equipment adjustment, as necessary. That is, this type refers to operating the same equipment "instead of" the refrigerant. As a method of "replacement" of this type, there may be "simple (drop in) replacement", "approximately simple (neutral drop in) replacement", and "update (refresh)" in order of the degree of change and adjustment required for replacement with the second refrigerant.
As a second type, equipment designed to operate using a second refrigerant, which is carried with the second refrigerant and used for the same purpose as the existing purpose of the first refrigerant, is also encompassed within the term "alternative". This type is meant to "replace" the refrigerant to provide the same purpose.
In the present specification, the term "refrigerator" refers to all devices that take heat from an object or space to lower the temperature than the surrounding outside air and maintain the low temperature. In other words, a refrigerator is a conversion device that obtains energy from the outside to convert energy in order to transfer heat from a low-temperature object to a high-temperature object.
In the present specification, the term "WCF micro-ignition" as used herein means that the combustion rate of the most inflammable composition (WCF) is 10cm/s or less according to the American ANSI/ASHRAE 34-2013 standard. In the present specification, the term "ASHRAE micro-combustion" as the refrigerant means that the combustion rate of the WCF is 10cm/s or less, the combustion rate of the most flammable fractionation composition (WCFF) determined by a leak test in use and storage/transportation of ANSI/ASHRAE 34-2013 by using the WCF is 10cm/s or less, and the combustibility classification of the american ANSI/ASHRAE 34-2013 standard is judged as "class 2L".
1.Refrigerant
1.1Refrigerant composition
The refrigerant of the present invention contains CO2And a mixed refrigerant of R32, HFO-1132(E) and R1234 yf.
The refrigerant of the present invention has various properties that are desirable as an alternative refrigerant for R410A, such as having a cooling capacity equivalent to that of R410A, having sufficiently low GWP, and being slightly flammable.
As the refrigerant of the present invention, CO is mixed2And W and x, y and z are taken as mass% based on the sum of R32, HFO-1132(E) and R1234yf, respectively, in a 3-component composition diagram in which the sum of R32, HFO-1132(E) and R1234yf is (100-w) mass%, the coordinates (x, y, z) are within a range of a graph formed by connecting 7 points of point I, point J, point K, point L, point B ', point D, point C, curve IJ, curve JK, curve KL, line LB', line B 'D, line DC and line CI, or on the line segment (excluding points on line B' D and line CI),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point L (51.7,28.9, 19.4-w),
Point B "(-1.5278 w)2+2.75w+50.5,0.0,1.5278w2－3.75w+49.5)、
Point D (-2.9167 w +40.317,0.0,1.9167w +59.683),
Point C (0.0, -4.9167 w +58.317,3.9167w +41.683),
when w is more than 1.2 and less than or equal to 4.0, the curve is in the range of a graph formed by connecting 7 points of the point I, the point J, the point K, the point L, the point B ', the point D and the point C, the curve JK, the curve KL, the straight line LB', the straight line B 'D, the straight line DC and the straight line CI, or the line segment (wherein, the points on the straight line B' D and the straight line CI are not included),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point L (51.7,28.9, 19.4-w),
Point B "(51.6,0.0, 48.4-w),
Point D (-2.8226 w +40.211,0.0,1.8226w +59.789),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w+41.553)，
When w is more than 4.0 and less than or equal to 7.0, the curve is in the range of a graph formed by connecting 7 points of the point I, the point J, the point K, the point L, the point B ', the point D and the point C, the curve JK, the curve KL, the straight line LB', the straight line B 'D, the straight line DC and the straight line CI, or the line segment (wherein, the points on the straight line B' D and the straight line CI are not included),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point L (51.7,28.9, 19.4-w),
Point B "(51.6,0.0, 48.4-w),
Point D (-2.8 w +40.1,0.0,1.8w +59.9),
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w +41.7), and,
curve IJ is represented by coordinates (x,0.0236 x)2－1.716x+72,－0.0236x2+0.716x + 28-w) represents,
curve JK consists of coordinates (x,0.0095 x)2－1.2222x+67.676,－0.0095x2+0.2222x + 32.324-w),
the curve KL is represented by the coordinates (x,0.0049 x)2－0.8842x+61.488,－0.0049x2-0.1158 x + 38.512-w).
The refrigerant of the present invention has a freezing capacity ratio based on R410A of 80% or more, a GWP of 350 or less, and a WCF micro-ignition.
As the refrigerant of the present invention, CO is mixed2And R32, HFO-1132(E) and R1234yf are w and x, y and z, respectively, the total of R32, HFO-1132(E) and R1234yf is (100-w) mass%, preferably coordinates (x, y, z)
When w is more than 0 and less than or equal to 1.2, the curve IJ and the curve JK respectively connecting 5 points of the point I, the point J, the point K, the point F and the point C, and the line KF, the line FC and the line CI are in the range of the graph or on the line segment (wherein, the points on the line CI are not included),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Points F (-0.0833 w +36.717, -4.0833 w +5.1833,3.1666w +58.0997),
Point C (0.0, -4.9167 w +58.317,3.9167w +41.683),
when w is more than 1.2 and less than or equal to 1.3, the curve IJ and the curve JK respectively connecting 5 points of the point I, the point J, the point K, the point F and the point C, and the line KF, the line FC and the line CI are in the range of the graph or on the line segment (wherein, the points on the line CI are not included),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point F (36.6, -3 w +3.9,2w +59.5),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w+41.553)，
When w is more than 1.3 and less than or equal to 4.0, the curve IJ and the curve JK respectively connecting 6 points of the point I, the point J, the point K, the point B ', the point D and the point C, and the straight line KB ', the straight line B ' D, the straight line DC and the straight line CI are in the range of the graph or on the line segment (wherein, the points on the straight line CI are not included),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point B' (36.6,0.0, -w +63.4),
Point D (-2.8226 w +40.211,0.0,1.8226w +59.789),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w+41.553)，
When w is more than 4.0 and less than or equal to 7.0, the curve IJ and the curve JK respectively connecting 6 points of the point I, the point J, the point K, the point B ', the point D and the point C, and the straight line KB ', the straight line B ' D, the straight line DC and the straight line CI are within the range of the graph or on the line segment (wherein, the points on the straight line CI are not included),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point K (36.8,35.6, 27.6-w),
Point B' (36.6,0.0, -w +63.4),
Point D (-2.8 w +40.1,0.0,1.8w +59.9),
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w +41.7, and,
curve IJ is represented by coordinates (x,0.0236 x)2－1.716x+72,－0.0236x2+0.716x + 28-w) represents,
curve JK consists of coordinates (x,0.0095 x)2－1.2222x+67.676,－0.0095x2+0.2222x + 32.324-w). When the refrigerant of the present invention satisfies the above conditions, the refrigerant has a freezing capacity ratio of 80% or more based on R410A, a GWP of 250 or less, and a WCF of slight combustion.
As the refrigerant of the present invention, CO is mixed2And R32, HFO-1132(E) and R1234yfWhen the sum of mass% is w and x, y and z, respectively, in the 3-component composition diagram where the sum of R32, HFO-1132(E) and R1234yf is (100-w) mass%, the coordinates (x, y, z) are preferred
When w is more than 0 and less than or equal to 1.2, the curve IJ and the curve JK respectively connecting 4 points of the point I, the point J, the point E and the point C and the line KF, the line FC and the line CI are in the range of the graph or on the line segment (wherein, the points on the line CI are not included),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point E (18.2, -1.1111 w)2－3.1667w+31.9,1.1111w2+2.1667w+49.9)、
Point C (0.0, -4.9167 w +58.317,3.9167w +41.683),
when w is more than 1.2 and less than or equal to 4.0, the curve IJ and the curve JK respectively connecting 4 points of the point I, the point J, the point E and the point C and the line KF, the line FC and the line CI are in the range of the graph or on the line segment (wherein, the points on the line CI are not included),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point E (-0.0365 w +18.26,0.0623 w)2－4.5381w+31.856,－0.0623w2+3.5746w+49.884)、
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w+41.553)，
When w is more than 4.0 and less than or equal to 7.0, the curve IJ and the curve JK respectively connecting 4 points of the point I, the point J, the point E and the point C and the line KF, the line FC and the line CI are in the range of the graph or on the line segment (wherein, the points on the line CI are not included),
point I (0.0,72.0, 28.0-w),
Point J (18.3,48.5, 33.2-w),
Point E (18.1,0.0444 w)2－4.3556w+31.411,－0.0444w2+3.3556w+50.489)、
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w +41.7), and,
curve IJ is represented by coordinates (x,0.0236 x)2－1.716x+72,－0.0236x2+0.716x + 28-w). When the refrigerant of the present invention satisfies the above conditions, the refrigerant has a freezing capacity ratio of 80% or more based on R410A, a GWP of 125 or less, and a WCF of low flammability.
As the refrigerant of the present invention, CO is mixed2And R32, HFO-1132(E) and R1234yf are w and x, y and z, respectively, the total of R32, HFO-1132(E) and R1234yf is (100-w) mass%, preferably coordinates (x, y, z)
When w is more than 0 and less than or equal to 0.6, the curve GO and the curve OP respectively connecting the 5 points of the point G, the point O, the point P, the point B and the point D, and the line PB ', the line B ' D and the line DG are in the range of the graph enclosed by the curve or the line segment (wherein, the points on the line B ' D are not included),
point G (-5.8333 w)2－3.1667w+22.2,7.0833w2+1.4167w+26.2,－1.25w2+0.75w+51.6)、
Point O (36.8,0.8333 w)2+1.8333w+22.6,－0.8333w2－2.8333w+40.6)、
Point P (51.7,1.1111 w)2+20.5,－1.1111w2－w+27.8)、
Point B "(-1.5278 w)2+2.75w+50.5,0.0,1.5278w2－3.75w+49.5)、
Point D (-2.9167 w +40.317,0.0,1.9167w +59.683),
when w is more than 0.6 and less than or equal to 1.2, the curve is in the range of a graph formed by connecting 6 points of the point G, the point N, the point O, the point P, the point B and the point D, the curve NO and the curve OP, and the line PB ', the line B ' D and the line DG or on the line segment (wherein, the point on the line B ' D is not included),
point G (-5.8333 w)2－3.1667w+22.2,7.0833w2+1.4167w+26.2,－1.25w2+0.75w+51.6)、
Point N (18.2,0.2778 w)2+3w+27.7,－0.2778w2－4w+54.1)、
Point O (36.8,0.8333 w)2+1.8333w+22.6,－0.8333w2－2.8333w+40.6)、
Point P (51.7,1.1111 w)2+20.5,－1.1111w2－w+27.8)、
Point B "(-1.5278 w)2+2.75w+50.5,0.0,1.5278w2－3.75w+49.5)、
Point D (-2.9167 w +40.317,0.0,1.9167w +59.683), and,
the curve GO is represented by the coordinates (x, (0.00487 w) when w is more than 0 and less than or equal to 0.62－0.0059w+0.0072)x2+(－0.279w2+0.2844w－0.6701)x+3.7639w2-0.2467 w +37.512,100-w-x-y),
the curve GN is represented by the coordinates (x, (0.0122 w) when w is more than 0.6 and less than or equal to 1.22－0.0113w+0.0313)x2+(－0.3582w2+0.1624w－1.4551)x+2.7889w2+3.7417w +43.824,100-w-x-y),
the curve NO is represented by the coordinates (x, (0.00487 w) when w is more than 0.6 and less than or equal to 1.22－0.0059w+0.0072)x2+(－0.279w2+0.2844w－0.6701)x+3.7639w2-0.2467 w +37.512,100-w-x-y),
when the curve OP is more than 0 and less than or equal to 1.2, the curve consists of coordinates (x, (0.0074 w)2－0.0133w+0.0064)x2+(－0.5839w2+1.0268w－0.7103)x+11.472w2-17.455 w +40.07,100-w-x-y),
when W is more than 1.2 and less than or equal to 4.0, the curve is within the range of a graph formed by 8 points of the point M, the point W, the point N, the point O, the point P, the point B ', the point D and the point C, the curve WN, the curve NO and the curve OP, the straight line PB', the straight line B 'D, the straight line DC and the straight line CM, or on the line segment (excluding the points on the straight line B' D and the straight line CM),
point M (0.0, -0.3004 w)2+2.419w+55.53,0.3004w2－3.419w+44.47)、
Point W (10.0, -0.3645W)2+3.5024w+34.422,0.3645w2－4.5024w+55.57)、
Point N (18.2, -0.3773 w)2+3.319w+28.26,0.3773w2－4.319w+53.54)、
Point O (36.8, -0.1392 w)2+1.4381w+24.475,0.1392w2+0－2.4381w+38.725)、
Point P (51.7, -0.2381 w)2+1.881w+20.186,0.2381w2－2.881w+28.114)、
Point B "(51.6,0.0, -w +48.4),
Point D (-2.8226 w +40.211,0.0,1.8226w +59.789),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w +41.553), and,
the curve MW is represented by the coordinates (x, (0.0043 w)2－0.0359w+0.1509)x2+(－0.0493w2+0.4669w－3.6193)x－0.3004w2+2.419w +55.53,100-w-x-y),
the curve WN is represented by the coordinates (x, (0.0055 w)2－0.0326w+0.0665)x2+(－0.1571w2+0.8981w－2.6274)x+0.6555w2-2.2153 w +54.044,100-w-x-y),
curve NO consists of the coordinates (x, (-0.00062 w)2+0.0036w+0.0037)x2+(0.0375w2－0.239w－0.4977)x－0.8575w2+6.4941w +36.078,100-w-x-y),
the curve OP is composed of coordinates (x, (-0.000463 w)2+0.0024w－0.0011)x2+(0.0457w2－0.2581w－0.075)x－1.355w2+8.749w +27.096,100-w-x-y),
when W is greater than 4.0 and less than or equal to 7.0, the curve is within the range of a graph formed by 8 points of the point M, the point W, the point N, the point O, the point P, the point B ', the point D and the point C, the curve WN, the curve NO and the curve OP, and the line PB', the line B 'D, the line DC and the line CM, or on the line segment (excluding the points on the line B' D and the line CM),
point M (0.0, -0.0667 w)2+0.8333w+58.133,0.0667w2－1.8333w+41.867)、
Point W (10.0, -0.0667W)2+1.1w+39.267,0.0667w2－2.1w+50.733)、
Point N (18.2, -0.0889 w)2+1.3778w+31.411,0.0889w2－2.3778w+50.389)、
Point O (36.8, -0.0444 w)2+0.6889w+25.956,0.0444w2－1.6889w+37.244)、
Point P (51.7, -0.0667 w)2+0.8333w+21.633,0.0667w2－1.8333w+26.667)、
Point B "(51.6,0.0, -w +48.4),
Point D (-2.8 w +40.1,0.0,1.8w +59.9),
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w +41.7), and,
the curve MW is represented by the coordinates (x, (0.00357 w)2－0.0391w+0.1756)x2+(－0.0356w2+0.4178w－3.6422)x－0.0667w2+0.8333w +58.103,100-w-x-y),
the curve WN is composed of coordinates (x, (-0.002061 w)2+0.0218w－0.0301)x2+(0.0556w2－0.5821w－0.1108)x－0.4158w2+4.7352w +43.383,100-w-x-y),
curve NO consists of the coordinates (x,0.0082 x)2+(0.0022w2－0.0345w－0.7521)x－0.1307w2+2.0247w +42.327,100-w-x-y),
the curve OP is composed of coordinates (x, (-0.0006258 w)2+0.0066w－0.0153)x2+(0.0516w2－0.5478w+0.9894)x－1.074w2+11.651w +10.992,100-w-x-y). When the refrigerant of the present invention satisfies the above conditions, the refrigerant has a freezing capacity ratio of 80% or more based on R410A, a GWP of 350 or less, and an ASHRAE micro-ignition.
As the refrigerant of the present invention, CO is mixed2And when w and x, y and z are mass% based on the sum of R32, HFO-1132(E) and R1234yf, respectively, coordinates (x, y, z) are preferred in a 3-component composition diagram in which the sum of R32, HFO-1132(E) and R1234yf is (100-a) mass%
When w is more than 0 and less than or equal to 0.6, the curve GO connecting 3 points OF the point G, the point O and the point F and the line OF and the line FG are within the range OF the graph or on the line segment,
point G (-5.8333 w)2－3.1667w+22.2,7.0833w2－1.4167w+26.2,－1.25w2+0.75w+51.6)、
Point O (36.8,0.8333 w)2+1.8333w+22.6,－0.8333w2－2.8333w+40.6)、
Point F (-0.0833 w +36.717, -4.0833 w +5.1833,3.1666w +58.0997), and,
curve GO consists of coordinates (x, (0.00487 w)2－0.0059w+0.0072)x2+(－0.279w2+0.2844w－0.6701)x+3.7639w2-0.2467 w +37.512,100-w-x-y),
when w is more than 0.6 and less than or equal to 1.2, the curve is within the range OF a graph formed by a curve GN and a curve NO, which respectively connect 4 points OF a point G, a point N, a point O and a point F, and a straight line OF and a straight line FG, or on the line segment,
point G (-5.8333 w)2－3.1667w+22.2,7.0833w2－1.4167w+26.2,－1.25w2+0.75w+51.6)、
Point N (18.2,0.2778 w)2+3.0w+27.7,－0.2.778w2－4.0w+54.1)、
Point O (36.8,0.8333 w)2+1.8333w+22.6,－0.8333w2－2.8333w+40.6)、
Point F (-0.0833 w +36.717, -4.0833 w +5.1833,3.1666w +58.0997), and,
the curve GN is represented by the coordinates (x, (0.0122 w) when w is more than 0.6 and less than or equal to 1.22－0.0113w+0.0313)x2+(－0.3582w2+0.1624w－1.4551)x+2.7889w2+3.7417w +43.824,100-w-x-y),
the curve NO is represented by the coordinates (x, (0.00487 w) when w is more than 0.6 and less than or equal to 1.22－0.0059w+0.0072)x2+(－0.279w2+0.2844w－0.6701)x+3.7639w2-0.2467 w +37.512,100-w-x-y),
when W is 1.2 < w.ltoreq.1.3, the curve is within the range OF a graph formed by 6 points OF a point M, a point W, a point N, a point O, a point F, and a point C, a curve MW, a curve WN, a curve NO, a straight line OF, a straight line FC, and a straight line CM, or on the line segment (excluding the point on the straight line CM),
point M (0.0, -0.3004 w)2+2.419w+55.53,0.3004w2－3.419w+44.47)、
Point W (10.0, -0.3645W)2+3.5024w+34.422,0.3645w2－4.5024w+55.578)、
Point N (18.2, -0.3773 w)2+3.319w+28.26,0.3773w2－4.319w+53.54)、
Point O (36.8, -0.1392 w)2－1.4384w+24.475,0.1392w2－2.4381w+38.725)、
Point F (36.6, -3 w +3.9,2w +59.5),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w +41.553), and,
the curve MW is represented by the coordinates (x, (0.0043 w)2－0.0359w+0.1509)x2+(－0.0493w2+0.4669w－3.6193)x－0.3004w2+2.419w +55.53,100-w-x-y),
the curve WN is represented by the coordinates (x, (0.0055 w)2－0.0326w+0.0665)x2+(－0.1571w2+0.8981w－2.6274)x+0.6555w2-2.2153 w +54.044,100-w-x-y),
curve NO consists of the coordinates (x, (-0.00062 w)2+0.0036w+0.0037)x2+(0.0375w2－0.239w－0.4977)x－0.8575w2+6.4941w +36.078,100-w-x-y),
when W is more than 1.3 and less than or equal to 4.0, the curve MW, WN, NO, OB ', B' and DC 'respectively connecting 7 points of the points M, W, N, O, B', D and C, and the line OB ', B' D, DC and CM are within the range of the graph or on the line segment (excluding the point on the line CM),
point M (0.0, -0.3004 w)2+2.419w+55.53,0.3004w2－3.419w+44.47)、
Point W (10.0, -0.3645W)2+3.5024w+34.422,0.3645w2－4.5024w+55.578)、
Point N (18.2, -0.3773 w)2+3.319w+28.26,0.3773w2－4.319w+53.54)、
Point O (36.8, -0.1392 w)2－1.4384w+24.475,0.1392w2－2.4381w+38.725)、
Point B' (36.6,0.0, -w +63.4),
Point D (-2.8226 w +40.211,0.0,1.8226w +59.789),
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w +41.553), and,
the curve MW is represented by the coordinates (x, (0.0043 w)2－0.0359w+0.1509)x2+(－0.0493w2+0.4669w－3.6193)x－0.3004w2+2.419w +55.53,100-w-x-y),
the curve WN is represented by the coordinates (x, (0.0055 w)2－0.0326w+0.0665)x2+(－0.1571w2+0.8981w－2.6274)x+0.6555w2-2.2153 w +54.044,100-w-x-y),
curve NO consists of the coordinates (x, (-0.00062 w)2+0.0036w+0.0037)x2+(0.0375w2－0.239w－0.4977)x+(－0.8575w2+6.4941w +36.078), 100-w-x-y),
when W is more than 4.0 and less than or equal to 7.0, the curve MW, WN, NO, OB ', B' and DC 'respectively connecting 7 points of the points M, W, N, O, B', D and C, and the line OB ', B' D, DC and CM are within the range of the graph or on the line segment (excluding the point on the line CM),
point M (0.0, -0.0667 w)2+0.8333w+58.133,0.0667w2－1.8333w+41.867)、
Point W (10.0, -0.0667W)2+1.1w+39.267,0.0667w2－2.1w+50.733)、
Point N (18.2, -0.0889 w)2+1.3778w+31.411,0.0889w2－2.3778w+50.389)、
Point O (36.8, -0.0444 w)2+0.6889w+25.956,0.0444w2－1.6889w+37.244)、
Point B' (36.6,0.0, -w +63.4),
Point D (-2.8 w +40.1,0.0,1.8w +59.9),
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w +41.7), and,
the curve MW is represented by the coordinates (x, (0.00357 w)2－0.0391w+0.1756)x2+(－0.0356w2+0.4178w－3.6422)x－0.0667w2+0.8333w +58.103,100-w-x-y),
the curve WN is composed of coordinates (x, (-0.002061 w)2+0.0218w－0.0301)x2+(0.0556w2－0.5821w－0.1108)x－0.4158w2+4.7352w +43.383,100-w-x-y),
curve NO consists of the coordinates (x, (0.0082 x)2+(0.0022w2－0.0345w－0.7521)x－0.1307w2+2.0247w +42.327,100-w-x-y). When the refrigerant of the present invention satisfies the above conditions, the refrigerant has a freezing capacity ratio of 80% or more based on R410A, a GWP of 250 or less, and an ASHRAE micro-ignition.
As the refrigerant of the present invention, CO is mixed2And when w and x, y and z are mass% based on the sum of R32, HFO-1132(E) and R1234yf, respectively, coordinates (x, y, z) are preferred in a 3-component composition diagram in which the sum of R32, HFO-1132(E) and R1234yf is (100-a) mass%
When W is 1.2 < w.ltoreq.4.0, the curve MW and curve WN connecting the 5 points of M, W, N, E, and C, respectively, and the line NE, EC, and CM are within the range of a figure surrounded by the line or on the line segment (excluding the point on the line CM),
point M (0.0, -0.3004 w)2+2.419w+55.53,0.3004w2－3.419w+44.47)、
Point W (10.0, -0.3645W)2+3.5024w+34.422,0.3645w2－4.5024w+55.578)、
Point N (18.2, -0.3773 w)2+3.319w+28.26,0.3773w2－4.319w+53.54)、
Point E (-0.0365 w +18.26,0.0623 w)2－4.5381w+31.856,－0.0623w2+3.5746w+49.884)、
Point C (0.0,0.1081 w)2－5.169w+58.447,－0.1081w2+4.169w +41.553), and,
the curve MW is represented by the coordinates (x, (0.0043 w)2－0.0359w+0.1509)x2+(－0.0493w2+0.4669w－3.6193)x－0.3004w2+2.419w +55.53,100-w-x-y),
the curve WN is represented by the coordinates (x, (0.0055 w)2－0.0326w+0.0665)x2+(－0.1571w2+0.8981w－2.6274)x+0.6555w2-2.2153 w +54.044,100-w-x-y),
when W is greater than 4.0 and less than or equal to 7.0, the curve MW and WN connecting the 5 points of M, W, N, E, and C, respectively, and the line NE, EC, and CM are within the range of the graph or on the line segment (excluding the points on the line CM),
point M (0.0, -0.0667 w)2+0.8333w+58.133,0.0667w2－1.8333w+41.867)、
Point W (10.0, -0.0667W)2+1.1w+39.267,0.0667w2－2.1w+50.733)、
Point N (18.2, -0.0889 w)2+1.3778w+31.411,0.0889w2－2.3778w+50.389)、
Point E (18.1,0.0444 w)2－4.3556w+31.411,－0.0444w2+3.3556w+50.489)、
Point C (0.0,0.0667 w)2－4.9667w+58.3,－0.0667w2+3.9667w +41.7), and,
the curve MW is represented by the coordinates (x, (0.00357 w)2－0.0391w+0.1756)x2+(－0.0356w2+0.4178w－3.6422)x－0.0667w2+0.8333w +58.103,100-w-x-y),
the curve WN is composed of coordinates (x, (-0.002061 w)2+0.0218w－0.0301)x2+(0.0556w2－0.5821w－0.1108)x－0.4158w2+4.7352w +43.383,100-w-x-y). When the refrigerant of the present invention satisfies the above conditions, the refrigerant has a freezing capacity ratio of 80% or more based on R410A, a GWP of 125 or less, and an ASHRAE micro-ignition.
In a range not impairing the above-mentioned characteristics and effects, except for CO2And R32, HFO-1132(E) and R1234yf, the refrigerant of the present invention may contain other additional refrigerants. In this respect, the refrigerant of the present invention preferably contains CO in the entire refrigerant2And R32, HFO-1132(E) and R1234yf in total at least 99.5 mass%, more preferably at least 99.75 mass%, furtherThe content of the compound in one step is preferably 99.9% by mass or more.
The additional refrigerant is not particularly limited and can be selected widely. As the additional refrigerant, the mixed refrigerant may contain one kind alone, or may contain two or more kinds.
1.2Use of
The refrigerant of the present invention can be preferably used as a working fluid for refrigerators.
The compositions of the present invention are suitable for use as a replacement refrigerant for R410A.
2.Refrigerant composition
The refrigerant composition of the present invention contains at least the refrigerant of the present invention, and can be used for the same purpose as the refrigerant of the present invention. The refrigerant composition of the present invention can be used for obtaining a working fluid for a refrigerator by mixing at least a refrigerator oil.
The refrigerant composition of the present invention contains at least one other component in addition to the refrigerant of the present invention. The refrigerant composition of the present invention may contain at least one of the following other components as required. As described above, when the refrigerant composition of the present invention is used as a working fluid for a refrigerator, it is usually used after being mixed with at least refrigerator oil. Therefore, the refrigerant composition of the present invention preferably contains substantially no refrigerating machine oil. Specifically, the refrigerant composition of the present invention preferably contains the refrigerating machine oil in an amount of 0 to 1% by mass, more preferably 0 to 0.1% by mass, based on the entire refrigerant composition.
2.1Water (W)
The refrigerant composition of the present invention may contain a trace amount of water. The water content in the refrigerant composition is preferably 0.1 mass% or less with respect to the entire refrigerant. By containing a small amount of water in the refrigerant composition, the intramolecular double bonds of the unsaturated fluorocarbon compound that can be contained in the refrigerant can be stabilized, and the unsaturated fluorocarbon compound is less likely to be oxidized, thereby improving the stability of the refrigerant composition.
2.2Tracer agent
When the refrigerant composition of the present invention is diluted, contaminated, or otherwise altered, a tracer may be added to the refrigerant composition of the present invention at a detectable concentration so that the alteration can be tracked.
The refrigerant composition of the present invention may contain one kind of tracer alone, or two or more kinds of tracers.
The tracer is not particularly limited, and can be appropriately selected from commonly used tracers. It is preferred to select as the tracer a compound that does not form impurities that are inevitably mixed into the refrigerant of the present invention.
Examples of the tracer include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, bromides, iodides, alcohols, aldehydes, ketones, and dinitrogen monoxide (N)2O), and the like. As tracers, hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrofluorocarbons, hydrochlorocarbons, hydrofluorocarbons and fluoroethers are particularly preferred.
The following compounds are particularly preferable as the above tracer.
FC-14 (tetrafluoromethane, CF)4)
HCC-40 (chloromethane, CH)3Cl)
HFC-23 (trifluoromethane, CHF)3)
HFC-41 (fluoromethane, CH)3Cl)
HFC-125 (pentafluoroethane, CF)3CHF2)
HFC-134a (1,1,1, 2-tetrafluoroethane, CF)3CH2F)
HFC-134(1,1,2, 2-tetrafluoroethane, CHF)2CHF2)
HFC-143a (1,1, 1-trifluoroethane, CF)3CH3)
HFC-143(1,1, 2-trifluoroethane, CHF)2CH2F)
HFC-152a (1, 1-difluoroethane, CHF)2CH3)
HFC-152(1, 2-difluoroethane, CH)2FCH2F)
HFC-161 (fluoroethane, CH)3CH2F)
HFC-245fa (1,1,1,3, 3-pentafluoropropane, CF)3CH2CHF2)
HFC-236fa (1,1,1,3,3, 3-hexafluoropropane, CF)3CH2CF3)
HFC-236ea (1,1,1,2,3, 3-hexafluoropropane, CF)3CHFCHF2)
HFC-227ea (1,1,1,2,3,3, 3-heptafluoropropane, CF)3CHFCF3)
HCFC-22 (chlorodifluoromethane, CHClF)2)
HCFC-31 (chlorofluoromethane, CH)2ClF)
CFC-1113 (chlorotrifluoroethylene, CF)2＝CClF)
HFE-125 (trifluoromethyl-difluoromethyl ether, CF)3OCHF2)
HFE-134a (trifluoromethyl-fluoromethyl ether, CF)3OCH2F)
HFE-143a (trifluoromethyl-methyl ether, CF)3OCH3)
HFE-227ea (trifluoromethyl-tetrafluoroethyl ether, CF)3OCHFCF3)
HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF)3OCH2CF3)
The tracer compounds may be present in the refrigerant composition at a combined concentration of from about 10 parts per million (ppm) by weight to about 1000 ppm. Preferably, the tracer compounds are present in the refrigerant composition at a total concentration of from about 30ppm to about 500ppm, and most preferably the tracer compounds are present in the refrigerant composition at a total concentration of from about 50ppm to about 300 ppm.
2.3Ultraviolet fluorescent dye
The refrigerant composition of the present invention may contain one kind of ultraviolet fluorescent dye alone, or two or more kinds of ultraviolet fluorescent dyes.
The ultraviolet fluorescent dye is not particularly limited, and can be appropriately selected from commonly used ultraviolet fluorescent dyes.
Examples of the ultraviolet fluorescent dye include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thianthrene, benzoxanthene, fluorescein, and derivatives thereof. As the ultraviolet fluorescent dye, one or both of naphthalimide and coumarin are particularly preferable.
2.4Stabilizer
The refrigerant composition of the present invention may contain one kind of the stabilizer alone, or two or more kinds of the stabilizers may be contained.
The stabilizer is not particularly limited, and can be appropriately selected from conventional stabilizers.
Examples of the stabilizer include nitro compounds, ethers, and amines.
Examples of the nitro compound include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.
Examples of the ethers include 1, 4-dioxane and the like.
Examples of the amines include 2,2,3,3, 3-pentafluoropropylamine and diphenylamine.
Further, butylhydroxyxylene, benzotriazole and the like can be cited.
The content of the stabilizer is not particularly limited, but is preferably 0.01 to 5% by mass, and more preferably 0.05 to 2% by mass, based on the entire refrigerant.
2.5Polymerization inhibitor
The refrigerant composition of the present invention may contain one kind of polymerization inhibitor alone, or two or more kinds of polymerization inhibitors.
The polymerization inhibitor is not particularly limited, and can be appropriately selected from conventional polymerization inhibitors.
Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, hydroquinone methyl ether, dimethyl-t-butylphenol, 2, 6-di-t-butyl-p-cresol, and benzotriazole.
The content of the polymerization inhibitor is not particularly limited, but is preferably 0.01 to 5% by mass, and more preferably 0.05 to 2% by mass, based on the entire refrigerant.
3.Working fluid containing refrigerator oil
The refrigerating machine oil-containing working fluid of the present invention contains at least the refrigerant or the refrigerant composition of the present invention and a refrigerating machine oil, and is used as a working fluid for a refrigerating machine. Specifically, the refrigerating machine oil-containing working fluid of the present invention is obtained by mixing a refrigerating machine oil used in a compressor of a refrigerating machine with a refrigerant or a refrigerant composition. The working fluid containing the refrigerating machine oil usually contains 10 to 50 mass% of the refrigerating machine oil.
3.1Refrigerating machine oil
The composition of the present invention may contain one kind of the refrigerating machine oil alone, or two or more kinds of the refrigerating machine oil.
The refrigerating machine oil is not particularly limited, and can be appropriately selected from conventional refrigerating machine oils. In this case, if necessary, a more excellent refrigerating machine oil can be appropriately selected from the viewpoint of improving the compatibility (miscibility) with the mixture and the action of the mixture such as stability.
As the base oil of the refrigerator oil, for example, at least one selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE) is preferable.
The refrigerator oil may contain additives in addition to the base oil. The additive may be at least one selected from the group consisting of an antioxidant, an extreme pressure agent, an acid scavenger, an oxygen scavenger, a copper deactivator, a rust preventive, an oiliness agent, and a defoaming agent.
The refrigerator oil preferably has a kinematic viscosity of 5 to 400cSt at 40 ℃ from the viewpoint of lubrication.
The refrigerating machine oil-containing working fluid of the present invention may further contain at least one additive, as required. Examples of the additives include the following compatibilizers.
3.2Compatibilizer
The working fluid containing a refrigerating machine oil of the present invention may contain one kind of the compatibilizer, or two or more kinds thereof.
The compatibilizer is not particularly limited, and can be appropriately selected from commonly used compatibilizers.
Examples of the compatibilizer include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorinated hydrocarbons (chlorocarbons), esters, lactones, aryl ethers, fluoroethers, and 1,1, 1-trifluoroalkanes. As the compatibilizer, polyoxyalkylene glycol ether is particularly preferable.
4.Method for operating refrigerator
The method for operating a refrigerator of the present invention is a method for operating a refrigerator using the refrigerant of the present invention.
Specifically, the method for operating a refrigerator according to the present invention includes a step of circulating the refrigerant according to the present invention in the refrigerator.
While the embodiments have been described above, it should be understood that various changes in form and details may be made therein without departing from the spirit and scope of the invention as claimed.
Examples
The following examples are given to explain the present invention in more detail. However, the present invention is not limited to these examples.
For CO2And R32, HFO-1132(E) and R1234yf were mixed and the combustion rate was measured in accordance with ANSI/ASHRAE 34-2013 standard. While changing CO2On the other hand, a composition showing a burning rate of 10cm/s was found. The compositions found are shown in tables 1 and 2.
The burning rate test was performed as follows using the apparatus shown in fig. 1. First, the mixed refrigerant used was 99.5% pure or more, and was degassed by repeating the cycle of freezing, pumping, and thawing until no trace of air was seen on the vacuum surface. The combustion rate was determined by the closed method. The initial temperature is the ambient temperature. Ignition is performed by generating an electric spark in the center of the sample chamber and between the electrodes. The discharge duration is 1.0 to 9.9ms and the ignition energy is typically about 0.1 to 1.0J. The propagation state of the flame is visualized by the schlieren method. A cylindrical container (inner diameter: 155mm, length: 198mm) having 2 light-transmitting acrylic windows was used as a sample chamber, and a xenon lamp was used as a light source. The streaked image of the flame was recorded at a framing speed of 600fps using a high-speed digital camera and stored in a PC.
The combustion velocity (Su (cm/s)) is represented by the volume of unburned gas consumed per unit time per unit area of the flame surface, and is calculated by the following equation.
Su＝Sb＊ρu/ρb
Sb: flame propagation speed (cm/s);
ρ u: adiabatic flame temperature (unburned);
ρ b: adiabatic flame temperature (burned).
Herein, Sb is obtained from a schlieren video image, ρ u is calculated from a measured temperature, and ρ b is calculated from combustion heat of combustion gas and a constant pressure specific heat.
The WCF concentration was determined by performing leak simulation using NIST Standard Reference Data Base Refleak Version 4.0, using the WCF concentration as an initial concentration.
[ Table 1]
0％CO2
0.6％CO2
1.2％CO2
1.3％CO2
2.5％CO2
4.0％CO2
5.5％CO2
7.0％CO2
[ Table 2]
0％CO2
0.6％CO2
1.2％CO2
1.3％CO2
[ Table 3]
2.5％CO2
4.0％CO2
5.5％CO2
7.0％CO2
Based on these results, CO is determined2And w and x, y and z are mass% based on the sum of R32, HFO-1132(E) and R1234yf, respectively, and WCF micro-ignition is achieved when coordinates (x, y, z) are on or below a line connecting points I, J, K and L, respectively, in the 3-component composition diagram of FIGS. 2 to 9 in which the sum of R32, HFO-1132(E) and R1234yf is (100-w) mass%.
It was also determined that ASHRAE micro-combustion occurred when the coordinates (x, y, z) were on the line connecting the points M, N, O and P or below the line in the 3-component composition diagram of fig. 2.
R32, HFO-1132(E) and R1234yf were mixed in the mass% amounts shown in tables 3 to 10 based on the total of the amounts of R32, HFO-1132(E) and R1234yf to prepare mixed refrigerants. For each of the refrigerant mixtures in tables 3 to 10, a refrigeration Coefficient of Performance (COP) ratio and a freezing capacity ratio were obtained based on R410.
The GWP of compositions containing a mixture of R1234yf and R410A (R32 ═ 50%/R125 ═ 50%) was evaluated based on the values of the fourth report of ipcc (international Panel on simulation change). Although not described as GWP, HFO-1132(E) has a GWP of 1, HFO-1132a (GWP of 1 or less) and HFO-1123(GWP of 0.3, described in patent document 1) are assumed to be used. The freezing capacity of a composition containing a mixture of R410A and HFO-1132(E), HFO-1123, R1234yf was determined by using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Reference Fluid Thermodynamic and Transport Properties Database) (Reference 9.0) and performing a theoretical calculation of the refrigeration cycle of a mixed refrigerant under the following conditions.
Evaporation temperature: 5 deg.C
Condensation temperature: 45 deg.C
Superheat temperature: 5K
Supercooling temperature: 5K
Ecomp(amount of compression work): 0.7 kWh.
These values are shown in tables 3 to 10 together with GWP for each mixed refrigerant. Wherein, tables 3 to 10 respectively represent CO2The concentration is 0 mass%, 0.6 mass%, 1.2 mass%, 1.3 mass%, 2.5 mass%, 4 mass%, 5.5 mass%, 7 mass%.
[ Table 4]
0％CO2
[ Table 5]
0.6％CO2
[ Table 6]
1.2％CO2
[ Table 7]
1.3％CO2
[ Table 8]
2.5％CO2
[ Table 9]
4％CO2
[ Table 10]
5.5％CO2
[ Table 11]
7％CO2
[ Table 12]
Item
Unit of
Comparative example 101
Comparative example 102
Comparative example 103
Example 103
Example 104
Comparative example 104
Comparative example 105
Comparative example 106
HFO-1132(E)
Mass%
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
R32
Mass%
78.8
68.8
58.8
48.8
38.8
28.8
18.8
8.8
R1234yf
Mass%
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
CO2
Mass%
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
GWP
-
532
465
398
331
264
197
130
63
Ratio of COP
% (relative to R410A)
101.3
101.2
101.1
101.0
101.0
101.3
102.0
102.8
Ratio of freezing capacities
% (relative to R410A)
108.5
104.1
99.2
93.6
87.2
80.1
72.2
63.1
Condensation slip
℃
1.1
1.6
2.2
3.1
4.3
5.8
7.4
8.4
Item
Unit of
Comparative example 107
Comparative example 108
Example 105
Example 106
Example 107
Comparative example 109
Comparative example 110
Comparative example 111
HFO-1132(E)
Mass%
20.0
20.0
20.0
20.0
20.0
20.0
20.0
30.0
R32
Mass%
68.8
58.8
48.8
38.8
28.8
18.8
8.8
58.8
R1234yf
Mass%
10.0
20.0
30.0
40.0
50.0
60.0
70.0
10.0
CO2
Mass%
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
GWP
-
465
398
331
264
197
130
62
398
Ratio of COP
% (relative to R410A)
100.6
100.5
100.4
100.3
100.4
100.9
101.8
100.0
Ratio of freezing capacities
% (relative to R410A)
108.6
103.9
98.6
92.6
85.8
78.2
69.6
108.3
Condensing slideMoving device
℃
1.1
1.7
2.5
3.5
4.8
6.4
7.7
1.2
Item
Unit of
Example 108
Example 109
Example 110
Example 111
Comparative example 112
Comparative example 113
Comparative example 114
Example 112
HFO-1132(E)
Mass%
30.0
30.0
30.0
30.0
30.0
40.0
40.0
40.0
R32
Mass%
48.8
38.8
28.8
18.8
8.8
48.8
38.8
28.8
R1234yf
Mass%
20.0
30.0
40.0
50.0
60.0
10.0
20.0
30.0
CO2
Mass%
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
GWP
-
331
263
196
129
62
330
263
196
Ratio of COP
% (relative to R410A)
99.9
99.8
99.8
100.1
100.8
99.4
99.3
99.3
Ratio of freezing capacities
% (relative to R410A)
103.2
97.5
91.0
83.7
75.6
107.5
102.0
95.8
Condensation slip
℃
1.8
2.7
3.8
5.2
6.6
1.3
2.0
2.9
Item
Unit of
Example 113
Example 114
Comparative example 115
Comparative example 116
Comparative example 117
Example 115
ComparisonExample 118
Comparative example 119
HFO-1132(E)
Mass%
40.0
40.0
50.0
50.0
50.0
50.0
60.0
60.0
R32
Mass%
18.8
8.8
38.8
28.8
18.8
8.8
28.8
18.8
R1234yf
Mass%
40.0
50.0
10.0
20.0
30.0
40.0
10.0
20.0
CO2
Mass%
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
GWP
-
129
62
263
196
129
62
195
128
Ratio of COP
% (relative to R410A)
99.5
100.0
99.0
98.9
99.0
99.4
98.7
98.7
Ratio of freezing capacities
% (relative to R410A)
88.9
81.1
106.2
100.3
93.7
86.2
104.5
98.2
Condensation slip
℃
4.1
5.4
1.4
2.2
3.2
4.3
1.5
2.4
Item
Unit of
Comparative example 120
Comparative example 121
Comparative example 122
Comparative example123
Example 116
Example 117
Example 118
Example 119
HFO-1132(E)
Mass%
60.0
70.0
70.0
80.0
15.0
15.0
15.0
15.0
R32
Mass%
8.8
18.8
8.8
8.8
48.8
46.3
43.8
41.3
R1234yf
Mass%
30.0
10.0
20.0
10.0
35.0
37.5
40.0
42.5
CO2
Mass%
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
GWP
-
61
128
61
61
331
314
297
281
Ratio of COP
% (relative to R410A)
99.0
98.5
98.8
98.6
100.7
100.7
100.6
100.6
Ratio of freezing capacities
% of (phase)For R410A)
91.0
102.4
95.5
99.7
96.1
94.7
93.1
91.6
Condensation slip
℃
3.3
1.7
2.5
1.9
2.8
3.0
3.3
3.6
Item
Unit of
Example 120
Example 121
Example 122
Example 123
Example 124
Example 125
Example 126
Example 127
HFO-1132(E)
Mass%
15.0
15.0
15.0
15.0
15.0
17.5
17.5
17.5
R32
Mass%
38.8
36.3
33.8
31.3
28.8
48.8
46.3
43.8
R1234yf
Mass%
45.0
47.5
50.0
52.5
55.0
32.5
35.0
37.5
CO2
Mass%
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
GWP
-
264
247
230
214
197
331
314
297
Ratio of COP
% (relative to R410A)
100.6
100.7
100.7
100.7
100.8
100.5
100.5
100.5
Ratio of freezing capacities
% (relative to R410A)
89.9
88.3
86.6
84.8
83.0
97.4
95.9
94.4
Condensation slip
℃
3.9
4.2
4.6
4.9
5.3
2.6
2.9
3.1
[ Table 13]
Item
Unit of
Example 128
Example 129
Example 130
Example 131
Example 132
Example 133
Example 134
Example 135
HFO-1132(E)
Mass%
17.5
17.5
17.5
17.5
17.5
17.5
17.5
20.0
R32
Mass%
41.3
38.8
36.3
33.8
31.3
28.8
26.3
46.3
R1234yf
Mass%
40.0
42.5
45.0
47.5
50.0
52.5
55.0
32.5
CO2
Mass%
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
GWP
-
281
264
247
230
213
197
180
314
Ratio of COP
% (relative to R410A)
100.5
100.5
100.5
100.5
100.6
100.6
100.7
100.4
Ratio of freezing capacities
% (relative to R410A)
92.9
91.3
89.6
87.9
86.2
84.4
82.6
97.1
Condensation slip
℃
3.4
3.7
4.0
4.3
4.7
5.1
5.4
2.7
Item
Unit of
Example 136
Example 137
Example 138
Example 139
Example 140
Example 141
Example 142
Example 143
HFO-1132(E)
Mass%
20.0
20.0
20.0
20.0
20.0
20.0
22.5
22.5
R32
Mass%
43.8
41.3
36.3
33.8
31.3
26.3
46.3
43.8
R1234yf
Mass%)
35.0
37.5
42.5
45.0
47.5
52.5
30.0
32.5
CO2
Mass%)
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
GWP
-
297
280
247
230
213
180
314
297
Ratio of COP
% of (phase)For R410A)
100.3
100.3
100.3
100.3
100.4
100.5
100.2
100.2
Ratio of freezing capacities
% (relative to R410A)
95.7
94.1
90.9
89.3
87.5
84.0
98.4
96.9
Condensation slip
℃
2.9
3.2
3.8
4.1
4.4
5.2
2.5
2.7
Item
Unit of
Example 144
Example 145
Example 146
Example 147
Example 148
Example 149
Example 150
Example 151
HFO-1132(E)
Mass%
22.5
22.5
22.5
22.5
22.5
22.5
22.5
22.5
R32
Mass%
41.3
38.8
36.3
33.8
31.3
28.8
26.3
23.8
R1234yf
Mass%
35.0
37.5
40.0
42.5
45.0
47.5
50.0
52.5
CO2
Mass%
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
GWP
-
280
264
247
230
213
197
180
163
Ratio of COP
% (relative to R410A)
100.2
100.2
100.2
100.2
100.2
100.3
100.3
100.4
Ratio of freezing capacities
% (relative to R410A)
95.4
93.8
92.2
90.6
88.9
87.1
85.3
83.5
Condensation slip
℃
3.0
3.3
3.6
3.9
4.2
4.5
4.9
5.3
Item
Unit of
Example 152
Example 153
Example 154
Example 155
Example 156
Example 157
Example 158
Example 159
HFO-1132(E)
Mass%
25.0
25.0
25.0
25.0
25.0
25.0
27.5
27.5
R32
Mass%
33.8
31.3
28.8
26.3
23.8
21.3
21.9
21.9
R1234yf
Mass%
40.0
42.5
45.0
47.5
50.0
52.5
45.0
47.5
CO2
Mass%
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
GWP
-
230
213
196
180
163
146
150
150
Ratio of COP
% (relative to R410A)
100.0
100.0
100.1
100.1
100.2
100.3
100.0
100.1
Ratio of freezing capacities
% (relative to R410A)
91.8
90.2
88.4
86.7
84.8
83.0
86.3
85.4
Condensation slip
℃
3.6
4.0
4.3
4.7
5.0
5.4
4.8
4.9
Item
Unit of
Example 160
Example 161
Example 162
Example 163
Example 164
HFO-1132(E)
Mass%
27.5
27.5
30.0
32.0
34.0
R32
Mass%
21.9
21.9
21.9
21.9
13.8
R1234yf
Mass%
50.0
52.5
52.5
51.0
51.0
CO2
Mass%
1.2
1.2
1.2
1.2
1.2
GWP
-
150
150
150
150
96
Ratio of COP
% (relative to R410A)
100.1
100.2
100.1
100.0
100.1
Ratio of freezing capacities
% (relative to R410A)
84.5
83.7
84.2
85.1
82.0
Condensation slip
℃
5.1
5.2
5.0
4.9
5.5
[ Table 14]
Item
Unit of
Comparative example 125
Comparative example 126
Comparative example 127
Example 166
Example 167
Example 168
Comparative example 128
Comparative example 129
HFO-1132(E)
Mass%
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
R32
Mass%
77.5
67.5
57.5
47.5
37.5
27.5
17.5
7.5
R1234yf
Mass%
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
CO2
Mass%
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
GWP
-
524
457
389
322
255
188
121
54
Ratio of COP
% (relative to R410A)
100.9
100.8
100.6
100.5
100.5
100.9
101.6
102.4
Ratio of freezing capacities
% (relative to R410A)
110.6
106.2
101.2
95.5
89.1
81.9
74.0
64.8
Condensation slip
℃
1.8
2.3
3.0
4.0
5.3
7.0
8.8
10.1
Item
Unit of
Comparative example 130
Comparative example 131
Example 169
Example 170
Example 171
Comparative example 132
Comparative example 133
Comparative example 134
HFO-1132(E)
Mass%
20.0
20.0
20.0
20.0
20.0
20.0
20.0
30.0
R32
Mass%
67.5
57.5
47.5
37.5
27.5
17.5
7.5
57.5
R1234yf
Mass%
10.0
20.0
30.0
40.0
50.0
60.0
70.0
10.0
CO2
Mass%
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
GWP
-
456
389
322
255
188
121
54
389
Ratio of COP
% (relative to R410A)
100.1
100.0
99.9
99.8
100.0
100.5
101.3
99.5
Ratio of freezing capacities
% (relative to R410A)
110.7
106.0
100.6
94.5
87.7
80.1
71.5
110.4
Condensation slip
℃
1.8
2.5
3.3
4.4
5.9
7.7
9.3
1.9
Item
Unit of
Example 172
Example 173
Example 174
Example 175
Comparative example 135
Comparative example 136
Comparative example 137
Example 176
HFO-1132(E)
Mass%
30.0
30.0
30.0
30.0
30.0
40.0
40.0
40.0
R32
Mass%
47.5
37.5
27.5
17.5
7.5
47.5
37.5
27.5
R1234yf
Mass%
20.0
30.0
40.0
50.0
60.0
10.0
20.0
30.0
CO2
Mass%
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
GWP
-
322
255
188
120
53
321
254
187
Ratio of COP
% (relative to R410A)
99.3
99.2
99.3
99.6
100.3
98.9
98.8
98.7
Ratio of freezing capacities
% (relative to R410A)
105.3
99.5
93.0
85.7
77.5
109.6
104.1
97.9
Condensation slip
℃
2.6
3.6
4.8
6.4
8.1
2.0
2.8
3.9
Item
Unit of
Example 177
Example 178
Comparative example 138
Comparative example 139
Comparative example 140
Example 179
Comparative example 141
Comparative example 142
HFO-1132(E)
Mass%
40.0
40.0
50.0
50.0
50.0
50.0
60.0
60.0
R32
Mass%
17.5
7.5
37.5
27.5
17.5
7.5
27.5
17.5
R1234yf
Mass%
40.0
50.0
10.0
20.0
30.0
40.0
10.0
20.0
CO2
Mass%
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
GWP
-
120
53
254
187
120
53
187
120
Ratio of COP
% (relative to R410A)
98.9
99.4
98.4
98.3
98.4
98.8
98.0
98.1
Ratio of freezing capacities
% (relative to R410A)
91.0
83.1
108.4
102.5
95.9
88.4
106.8
100.4
Condensation slip
℃
5.3
6.8
2.2
3.1
4.3
5.6
2.4
3.4
Item
Unit of
Example 180
Comparative example 143
Comparative example 144
Comparative example 145
Example 181
Example 182
Example 183
Example 184
HFO-1132(E)
Mass%
60.0
70.0
70.0
80.0
15.0
15.0
15.0
15.0
R32
Mass%
7.5
17.5
7.5
7.5
50.0
47.5
45.0
42.5
R1234yf
Mass%
30.0
10.0
20.0
10.0
32.5
35.0
37.5
40.0
CO2
Mass%
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
GWP
-
52
119
52
52
339
322
305
289
Ratio of COP
% (relative to R410A)
98.4
97.9
98.1
98.0
100.2
100.2
100.2
100.2
Ratio of freezing capacities
% (relative to R410A)
93.3
104.7
97.8
102.1
99.6
98.1
96.6
95.1
Condensation slip
℃
4.6
2.7
3.8
3.0
3.4
3.6
3.9
4.2
Item
Unit of
Example 185
Example 186
Example 187
Example 188
Example 189
Example 190
Example 191
Example 192
HFO-1132(E)
Mass%
15.0
15.0
15.0
15.0
15.0
15.0
15.0
17.5
R32
Mass%
40.0
37.5
35.0
32.5
30.0
27.5
25.0
50.0
R1234yf
Mass%
42.5
45.0
47.5
50.0
52.5
55.0
57.5
30.0
CO2
Mass%
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
GWP
-
272
255
238
222
205
188
171
339
Ratio of COP
% (relative to R410A)
100.2
100.2
100.2
100.2
100.3
100.4
100.5
100.1
Ratio of freezing capacities
% (relative to R410A)
93.5
91.9
90.2
88.5
86.7
84.9
83.0
100.8
Condensation slip
℃
4.5
4.8
5.2
5.6
6.0
6.4
6.9
3.2
[ Table 15]
Item
Unit of
Example 193
Example 194
Example 195
Example 196
Example 197
Example 198
Example 199
Example 200
HFO-1132(E)
Mass%
17.5
17.5
17.5
17.5
17.5
17.5
17.5
17.5
R32
Mass%
47.5
45.0
42.5
40.0
37.5
35.0
32.5
30.0
R1234yf
Mass%
32.5
35.0
37.5
40.0
42.5
45.0
47.5
50.0
CO2
Mass%
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
GWP
-
322
305
289
272
255
238
221
205
Ratio of COP
% (relative to R410A)
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.1
Ratio of freezing capacities
% (relative to R410A)
99.4
97.9
96.4
94.8
93.2
91.5
89.8
88.1
Condensation slip
℃
3.5
3.7
4.0
4.3
4.6
5.0
5.3
5.7
Item
Unit of
Example 201
Example 202
Example 203
Example 204
Example 205
Example 206
Example 207
Example 208
HFO-1132(E)
Mass%
17.5
17.5
17.5
20.0
20.0
20.0
20.0
20.0
R32
Mass%
27.5
25.0
22.5
50.0
45.0
42.5
40.0
35.0
R1234yf
Mass%
52.5
55.0
57.5
27.5
32.5
35.0
37.5
42.5
CO2
Mass%
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
GWP
-
188
171
154
339
305
289
272
238
Ratio of COP
% (relative to R410A)
100.2
100.3
100.4
99.9
99.9
99.8
99.8
99.8
Ratio of freezing capacities
% (relative to R410A)
86.3
84.4
82.6
102.0
99.2
97.7
96.1
92.9
Condensation slip
℃
6.2
6.6
7.0
3.1
3.5
3.8
4.1
4.7
Item
Unit of
Example 209
Example 210
Example 211
Example 212
Example 213
Example 214
Example 215
Example 216
HFO-1132(E)
Mass%
20.0
20.0
20.0
20.0
20.0
22.5
22.5
22.5
R32
Mass%
32.5
30.0
25.0
22.5
20.0
50.0
47.5
45.0
R1234yf
Mass%
45.0
47.5
52.5
55.0
57.5
25.0
27.5
30.0
CO2
Mass%
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
GWP
-
221
205
171
154
138
339
322
305
Ratio of COP
% (relative to R410A)
99.8
99.9
100.0
100.2
100.3
99.8
99.7
99.7
Ratio of freezing capacities
% (relative to R410A)
91.2
89.5
85.9
84.0
82.1
103.2
101.8
100.4
Condensation slip
℃
5.1
5.5
6.3
6.7
7.2
2.9
3.1
3.4
Item
Unit of
Example 217
Example 218
Example 219
Example 220
Example 221
Example 222
Example 223
Example 224
HFO-1132(E)
Mass%
22.5
22.5
22.5
22.5
22.5
22.5
22.5
22.5
R32
Mass%
42.5
40.0
37.5
35.0
32.5
30.0
27.5
25.0
R1234yf
Mass%
32.5
35.0
37.5
40.0
42.5
45.0
47.5
50.0
CO2
Mass%
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
GWP
-
288
272
255
238
221
205
188
171
Ratio of COP
% (relative to R410A)
99.7
99.7
99.7
99.7
99.7
99.7
99.8
99.8
Ratio of freezing capacities
% (relative to R410A)
98.9
97.4
95.8
94.2
92.5
90.8
89.0
87.2
Condensation slip
℃
3.6
3.9
4.2
4.5
4.9
5.2
5.6
6.0
Item
Unit of
Example 225
Example 226
Example 227
Example 228
Example 229
Example 230
Example 231
Example 232
HFO-1132(E)
Mass%
22.5
22.5
22.5
25.0
25.0
25.0
25.0
25.0
R32
Mass%
22.5
20.0
17.5
40.0
37.5
35.0
32.5
30.0
R1234yf
Mass%
52.5
55.0
57.5
32.5
35.0
37.5
40.0
42.5
CO2
Mass%
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
GWP
-
154
137
121
272
255
238
221
204
Ratio of COP
% (relative to R410A)
99.9
100.1
100.2
99.5
99.5
99.5
99.5
99.5
Ratio of freezing capacities
% (relative to R410A)
85.4
83.5
81.5
98.6
97.1
95.5
93.8
92.1
Condensation slip
℃
6.5
6.9
7.3
3.7
4.0
4.3
4.6
5.0
Item
Unit of
Example 233
Example 234
Example 235
Example 236
Example 237
Example 238
Example 239
Example 240
HFO-1132(E)
Mass%
25.0
25.0
25.0
25.0
25.0
27.5
27.5
27.5
R32
Mass%
27.5
25.0
22.5
20.0
17.5
32.5
30.0
27.5
R1234yf
Mass%
45.0
47.5
50.0
52.5
55.0
37.5
40.0
42.5
CO2
Mass%
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
GWP
-
188
171
154
137
121
221
204
188
Ratio of COP
% (relative to R410A)
99.6
99.6
99.7
99.9
100.0
99.4
99.4
99.4
Ratio of freezing capacities
% (relative to R410A)
90.4
88.6
86.8
84.9
83.0
95.1
93.4
91.7
Condensation slip
℃
5.4
5.7
6.2
6.6
7.0
4.4
4.7
5.1
[ Table 16]
Item
Unit of
Example 241
Example 242
Example 243
Example 244
Example 245
Example 246
Example 247
Example 248
HFO-1132(E)
Mass%
27.5
27.5
27.5
27.5
27.5
30.0
30.0
30.0
R32
Mass%
25.0
22.5
20.0
17.5
15.0
25.0
22.5
20.0
R1234yf
Mass%
45.0
47.5
50.0
52.5
55.0
42.5
45.0
47.5
CO2
Mass%
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
GWP
-
171
154
137
121
104
171
154
137
Ratio of COP
% (relative to R410A)
99.5
99.5
99.6
99.8
99.9
99.3
99.4
99.5
Ratio of freezing capacities
% (relative to R410A)
89.9
88.1
86.3
84.3
82.4
91.3
89.5
87.6
Condensation slip
℃
5.5
5.9
6.3
6.7
7.2
5.2
5.6
6.0
Item
Unit of
Example 249
Example 250
Example 251
Example 252
Example 253
Example 254
Example 255
Example 256
HFO-1132(E)
Mass%
30.0
30.0
32.5
32.5
32.5
32.5
35.0
35.0
R32
Mass%
15.0
12.5
20.0
17.5
15.0
12.5
15.0
12.5
R1234yf
Mass%
52.5
55.0
45.0
47.5
50.0
52.5
47.5
50.0
CO2
Mass%
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
GWP
-
104
87
137
120
104
87
104
87
Ratio of COP
% (relative to R410A)
99.7
99.9
99.3
99.4
99.5
99.7
99.3
99.5
Ratio of freezing capacities
% (relative to R410A)
83.8
81.8
88.9
87.1
85.1
83.1
86.5
84.5
Condensation slip
℃
6.8
7.3
5.7
6.1
6.5
7.0
6.2
6.6
Item
Unit of
Example 257
Example 258
Example 259
Example 260
Example 261
Example 262
Example 263
Example 264
HFO-1132(E)
Mass%
35.0
37.5
37.5
37.5
40.0
40.0
42.5
42.5
R32
Mass%
10.0
12.5
10.0
7.5
10.0
5.0
7.5
5.0
R1234yf
Mass%
52.5
47.5
50.0
52.5
47.5
52.5
47.5
50.0
CO2
Mass%
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
GWP
-
70
87
70
53
70
36
53
36
Ratio of COP
% (relative to R410A)
99.6
99.3
99.4
99.6
99.3
99.6
99.3
99.4
Ratio of freezing capacities
% (relative to R410A)
82.5
85.8
83.8
81.8
85.2
81.0
84.5
82.4
Condensation slip
℃
7.1
6.3
6.7
7.1
6.4
7.2
6.5
6.9
Item
Unit of
Example 265
Example 266
Example 267
Example 268
Example 269
Example 270
Example 271
HFO-1132(E)
Mass%
45.0
45.0
47.5
47.5
50.0
52.5
55.0
R32
Mass%
5.0
2.5
4.0
1.5
2.5
1.5
1.0
R1234yf
Mass%
47.5
50.0
46.0
48.5
45.0
43.5
41.5
CO2
Mass%
2.5
2.5
2.5
2.5
2.5
2.5
2.5
GWP
-
36
19
29
13
19
12
9
Ratio of COP
% (relative to R410A)
99.3
99.4
99.2
99.3
99.1
99.1
99.0
Ratio of freezing capacities
% (relative to R410A)
83.7
81.6
84.2
82.0
84.2
84.7
85.6
Condensation slip
℃
6.6
6.9
6.4
6.7
6.3
6.2
5.9
[ Table 17]
Item
Unit of
Comparative example 146
Comparative example 147
Comparative example 148
Example 272
Example 273
Example 274
Comparative example 149
Comparative example 150
HFO-1132(E)
Mass%
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
R32
Mass%
76.0
66.0
56.0
46.0
36.0
26.0
16.0
6.0
R1234yf
Mass%
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
514
446
379
312
245
178
111
44
Ratio of COP
% (relative to R410A)
100.3
100.2
100.1
100.0
100.0
100.4
101.2
102.0
Ratio of freezing capacities
% (relative to R410A)
113.0
108.6
103.5
97.8
91.3
84.1
76.1
66.8
Condensation slip
℃
2.5
3.1
3.9
5.0
6.4
8.3
10.4
12.2
Item
Unit of
Comparative example 146
Comparative example 147
Example 275
Example 276
Example 277
Example 278
Comparative example 153
Comparative example 154
HFO-1132(E)
Mass%
20.0
20.0
20.0
20.0
20.0
20.0
20.0
30.0
R32
Mass%
66.0
56.0
46.0
36.0
26.0
16.0
6.0
56.0
R1234yf
Mass%
10.0
20.0
30.0
40.0
50.0
60.0
70.0
10.0
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
446
379
312
245
178
111
44
379
Ratio of COP
% (relative to R410A)
99.6
99.5
99.3
99.2
99.4
100.0
100.9
98.9
Ratio of freezing capacities
% (relative to R410A)
113.1
108.4
103.0
96.8
89.9
82.3
73.7
112.9
Condensation slip
℃
2.6
3.3
4.2
5.5
7.1
9.2
11.2
2.7
Item
Unit of
Example 279
Example 280
Example 281
Example 282
Comparative example 155
Comparative example 156
Comparative example 157
Example 283
HFO-1132(E)
Mass%
30.0
30.0
30.0
30.0
30.0
40.0
40.0
40.0
R32
Mass%
46.0
36.0
26.0
16.0
6.0
46.0
36.0
26.0
R1234yf
Mass%
20.0
30.0
40.0
50.0
60.0
10.0
20.0
30.0
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
312
245
177
110
43
311
244
177
Ratio of COP
% (relative to R410A)
98.7
98.6
98.7
99.0
99.8
98.3
98.1
98.1
Ratio of freezing capacities
% (relative to R410A)
107.7
101.9
95.4
88.0
79.9
112.1
106.6
100.4
Condensation slip
℃
3.5
4.6
6.0
7.8
9.8
2.8
3.8
5.0
Item
Unit of
Example 284
Example 285
Comparative example 158
Comparative example 159
Example 286
Example 287
Comparative example 160
Comparative example 161
HFO-1132(E)
Mass%
40.0
40.0
50.0
50.0
50.0
50.0
60.0
60.0
R32
Mass%
16.0
6.0
36.0
26.0
16.0
6.0
26.0
16.0
R1234yf
Mass%
40.0
50.0
10.0
20.0
30.0
40.0
10.0
20.0
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
110
43
244
177
110
43
177
109
Ratio of COP
% (relative to R410A)
98.3
98.8
97.7
97.7
97.8
98.2
97.3
97.4
Ratio of freezing capacities
% (relative to R410A)
93.4
85.6
110.9
105.0
98.4
90.9
109.3
103.0
Condensation slip
℃
6.6
8.4
3.1
4.1
5.5
7.1
3.4
4.6
Item
Unit of
Example 288
Comparative example 162
Comparative example 163
Comparative example 164
Example 289
Example 290
Example 291
Example 292
HFO-1132(E)
Mass%
60.0
70.0
70.0
80.0
15.0
15.0
15.0
15.0
R32
Mass%
6.0
16.0
6.0
6.0
48.5
46.0
43.5
41.0
R1234yf
Mass%
30.0
10.0
20.0
10.0
32.5
35.0
37.5
40.0
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
42
109
42
42
329
312
295
279
Ratio of COP
% (relative to R410A)
97.7
97.2
97.4
97.2
99.7
99.6
99.6
99.6
Ratio of freezing capacities
% (relative to R410A)
95.9
107.3
100.5
104.9
101.9
100.4
98.9
97.4
Condensation slip
℃
6.0
3.8
5.1
4.3
4.3
4.6
4.9
5.2
Item
Unit of
Example 293
Example 294
Example 295
Example 296
Example 297
Example 298
Example 299
Example 300
HFO-1132(E)
Mass%
15.0
15.0
15.0
15.0
15.0
15.0
15.0
15.0
R32
Mass%
38.5
36.0
33.5
31.0
28.5
26.0
23.5
21.0
R1234yf
Mass%
42.5
45.0
47.5
50.0
52.5
55.0
57.5
60.0
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
262
245
228
211
195
178
161
144
Ratio of COP
% (relative to R410A)
99.6
99.6
99.6
99.7
99.8
99.9
100.0
100.2
Ratio of freezing capacities
% (relative to R410A)
95.8
94.1
92.4
90.7
88.9
87.1
85.2
83.3
Condensation slip
℃
5.6
5.9
6.3
6.8
7.2
7.7
8.2
8.7
[ Table 18]
Item
Unit of
Example 301
Example 302
Example 303
Example 304
Example 305
Example 306
Example 307
Example 308
HFO-1132(E)
Mass%
15.0
17.5
17.5
17.5
17.5
17.5
17.5
17.5
R32
Mass%
18.5
48.5
46.0
43.5
41.0
38.5
36.0
33.5
R1234yf
Mass%
62.5
30.0
32.5
35.0
37.5
40.0
42.5
45.0
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
128
329
312
295
278
262
245
228
Ratio of COP
% (relative to R410A)
100.4
99.5
99.5
99.4
99.4
99.4
99.4
99.4
Ratio of freezing capacities
% (relative to R410A)
81.3
103.1
101.7
100.2
98.7
97.1
95.5
93.8
Condensation slip
℃
9.3
4.1
4.4
4.7
5.0
5.3
5.7
6.1
Item
Unit of
Example 309
Example 310
Example 311
Example 312
Example 313
Example 314
Example 315
Example 316
HFO-1132(E)
Mass%
17.5
17.5
17.5
17.5
17.5
17.5
20.0
20.0
R32
Mass%
31.0
28.5
26.0
23.5
21.0
18.5
48.5
43.5
R1234yf
Mass%
47.5
50.0
52.5
55.0
57.5
60.0
27.5
32.5
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
211
195
178
161
144
127
329
295
Ratio of COP
% (relative to R410A)
99.5
99.5
99.6
99.8
99.9
100.1
99.3
99.3
Ratio of freezing capacities
% (relative to R410A)
92.1
90.3
88.5
86.7
84.8
82.8
104.4
101.5
Condensation slip
℃
6.5
7.0
7.4
7.9
8.4
9.0
4.0
4.5
Item
Unit of
Example 317
Example 318
Example 319
Example 320
Example 321
Example 322
Example 323
Example 324
HFO-1132(E)
Mass%
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
R32
Mass%
41.0
38.5
33.5
31.0
28.5
23.5
21.0
18.5
R1234yf
Mass%
35.0
37.5
42.5
45.0
47.5
52.5
55.0
57.5
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
278
262
228
211
195
161
144
127
Ratio of COP
% (relative to R410A)
99.3
99.2
99.3
99.3
99.3
99.5
99.6
99.8
Ratio of freezing capacities
% (relative to R410A)
100.0
98.4
95.2
93.5
91.7
88.1
86.2
84.3
Condensation slip
℃
4.8
5.1
5.8
6.2
6.7
7.6
8.1
8.6
Item
Unit of
Example 325
Example 326
Example 327
Example 328
Example 329
Example 330
Example 331
Example 332
HFO-1132(E)
Mass%
22.5
22.5
22.5
22.5
22.5
22.5
22.5
22.5
R32
Mass%
48.5
46.0
43.5
41.0
38.5
36.0
33.5
31.0
R1234yf
Mass%
25.0
27.5
30.0
32.5
35.0
37.5
40.0
42.5
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
329
312
295
278
262
245
228
211
Ratio of COP
% (relative to R410A)
99.2
99.2
99.1
99.1
99.1
99.1
99.1
99.1
Ratio of freezing capacities
% (relative to R410A)
105.6
104.2
102.7
101.3
99.7
98.1
96.5
94.8
Condensation slip
℃
3.8
4.0
4.3
4.6
4.9
5.2
5.6
6.0
Item
Unit of
Example 333
Example 334
Example 335
Example 336
Example 337
Example 338
Example 339
Example 340
HFO-1132(E)
Mass%
22.5
22.5
22.5
22.5
22.5
22.5
22.5
25.0
R32
Mass%
28.5
26.0
23.5
21.0
18.5
16.0
13.5
43.5
R1234yf
Mass%
45.0
47.5
50.0
52.5
55.0
57.5
60.0
27.5
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
194
178
161
144
127
111
94
295
Ratio of COP
% (relative to R410A)
99.1
99.2
99.3
99.4
99.5
99.7
99.9
99.0
Ratio of freezing capacities
% (relative to R410A)
93.1
91.3
89.5
87.7
85.8
83.8
81.8
104.0
Condensation slip
℃
6.4
6.8
7.3
7.8
8.3
8.8
9.3
4.1
Item
Unit of
Example 341
Example 342
Example 343
Example 344
Example 345
Example 346
Example 347
Example 348
HFO-1132(E)
Mass%
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
R32
Mass%
41.0
38.5
36.0
33.5
31.0
28.5
26.0
23.5
R1234yf
Mass%
30.0
32.5
35.0
37.5
40.0
42.5
45.0
47.5
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
278
261
245
228
211
194
178
161
Ratio of COP
% (relative to R410A)
98.9
98.9
98.9
98.9
98.9
99.0
99.0
99.1
Ratio of freezing capacities
% (relative to R410A)
102.5
101.0
99.4
97.8
96.1
94.4
92.7
90.9
Condensation slip
℃
4.4
4.7
5.0
5.4
5.7
6.1
6.5
7.0
[ Table 19]
Item
Unit of
Example 349
Example 350
Example 351
Example 352
Example 353
Example 354
Example 355
Example 356
HFO-1132(E)
Mass%
25.0
25.0
25.0
25.0
27.5
27.5
27.5
27.5
R32
Mass%
21.0
18.5
16.0
13.5
35.0
31.0
28.5
26.0
R1234yf
Mass%
50.0
52.5
55.0
57.5
35.0
37.5
40.0
42.5
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
144
127
110
94
238
211
194
178
Ratio of COP
% (relative to R410A)
99.2
99.3
99.5
99.7
98.8
98.8
98.8
98.8
Ratio of freezing capacities
% (relative to R410A)
89.1
87.2
85.2
83.2
99.4
97.4
95.8
94.0
Condensation slip
℃
7.5
8.0
8.5
9.0
5.0
5.5
5.9
6.3
Item
Unit of
Example 357
Example 358
Example 359
Example 360
Example 361
Example 362
Example 363
Example 364
HFO-1132(E)
Mass%
27.5
27.5
27.5
27.5
27.5
27.5
30.0
30.0
R32
Mass%
23.5
21.0
18.5
16.0
13.5
11.0
23.5
21.0
R1234yf
Mass%
45.0
47.5
50.0
52.5
55.0
57.5
42.5
45.0
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
161
144
127
110
94
77
161
144
Ratio of COP
% (relative to R410A)
98.9
99.0
99.1
99.2
99.4
99.6
98.7
98.8
Ratio of freezing capacities
% (relative to R410A)
92.3
90.4
88.6
86.7
84.7
82.6
93.6
91.8
Condensation slip
℃
6.7
7.2
7.6
8.1
8.7
9.2
6.4
6.9
Item
Unit of
Example 365
Example 366
Example 367
Example 368
Example 369
Example 400
Example 401
Example 402
HFO-1132(E)
Mass%
30.0
30.0
30.0
30.0
32.5
32.5
32.5
32.5
R32
Mass%
18.5
13.5
11.0
8.5
21.0
18.5
16.0
35.0
R1234yf
Mass%
47.5
52.5
55.0
57.5
42.5
45.0
47.5
50.0
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
127
94
77
60
144
127
110
239
Ratio of COP
% (relative to R410A)
98.9
99.2
99.3
99.5
98.6
98.7
98.8
99.1
Ratio of freezing capacities
% (relative to R410A)
89.9
86.1
84.1
82.0
93.1
91.3
89.4
94.0
Condensation slip
℃
7.3
8.3
8.8
9.3
6.6
7.0
7.5
5.5
Item
Unit of
Example 403
Example 404
Example 405
Example 406
Example 407
Example 408
Example 409
Example 410
HFO-1132(E)
Mass%
32.5
32.5
32.5
35.0
35.0
35.0
35.0
35.0
R32
Mass%
11.0
8.5
6.0
16.0
13.5
11.0
8.5
6.0
R1234yf
Mass%
52.5
55.0
57.5
45.0
47.5
50.0
52.5
55.0
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
77
60
43
110
93
77
60
43
Ratio of COP
% (relative to R410A)
99.1
99.3
99.5
98.6
98.7
98.9
99.1
99.3
Ratio of freezing capacities
% (relative to R410A)
85.5
83.4
81.3
90.8
88.8
86.9
84.8
82.8
Condensation slip
℃
8.5
9.0
9.5
7.2
7.6
8.1
8.6
9.1
Item
Unit of
Example 411
Example 412
Example 413
Example 414
Example 415
Example 416
Example 417
Example 418
HFO-1132(E)
Mass%
37.5
37.5
37.5
37.5
37.5
40.0
40.0
40.0
R32
Mass%
13.5
11.0
8.5
6.0
3.5
11.0
8.5
3.5
R1234yf
Mass%
45.0
47.5
50.0
52.5
55.0
45.0
47.5
52.5
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
93
77
60
43
26
76
60
26
Ratio of COP
% (relative to R410A)
98.6
98.7
98.9
99.0
99.2
98.5
98.7
99.0
Ratio of freezing capacities
% (relative to R410A)
90.2
88.2
86.2
84.2
82.0
89.6
87.6
83.4
Condensation slip
℃
7.3
7.8
8.3
8.8
9.2
7.5
7.9
8.9
Item
Unit of
Example 419
Example 420
Example 421
Example 422
Example 423
Example 424
Example 425
Example 426
HFO-1132(E)
Mass%
40.0
42.5
42.5
42.5
42.5
45.0
45.0
45.0
R32
Mass%
1.0
8.5
35.0
3.5
1.0
6.0
3.5
1.0
R1234yf
Mass%
55.0
45.0
47.5
50.0
52.5
45.0
47.5
50.0
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
9
60
239
26
9
43
26
9
Ratio of COP
% (relative to R410A)
99.2
98.5
98.8
98.8
99.0
98.5
98.6
98.8
Ratio of freezing capacities
% (relative to R410A)
81.2
88.9
95.6
84.8
82.6
88.3
86.2
84.0
Condensation slip
℃
9.3
7.6
5.0
8.5
9.0
7.8
8.2
8.7
[ Table 20]
Item
Unit of
Example 427
Example 428
Example 429
Example 430
Example 431
Example 432
HFO-1132(E)
Mass%
47.5
47.5
50.0
50.0
52.5
55.0
R32
Mass%
4.5
2.0
3.5
1.0
2.0
1.0
R1234yf
Mass%
44.0
46.5
42.5
45.0
41.5
40.0
CO2
Mass%
4.0
4.0
4.0
4.0
4.0
4.0
GWP
-
33
16
26
9
16
9
Ratio of COP
% (relative to R410A)
98.4
98.6
98.3
98.5
98.3
98.2
Ratio of freezing capacities
% (relative to R410A)
88.4
86.3
88.9
86.8
88.9
89.4
Condensation slip
℃
7.7
8.1
7.6
8.0
7.5
7.4
Based on these results, CO is determined2And R32, HFO-1132(E) and R1234yf, wherein w and x, y and z are mass% based on the sum of w and x, y and z, respectively, and when coordinates (x, y, z) are on the line of a straight line A 'B' in the 3-component composition diagrams of FIGS. 2 to 9 in which the sum of R32, HFO-1132(E) and R1234yf is (100-w), the GWP of the mixed refrigerant is 350; located further to the right than the line, the GWP of the mixed refrigerant is less than 350. Further, it is judged that, in the 3-component composition diagrams of fig. 2 to 9, when the coordinates (x, y, z) are on the line of the straight line a 'B', the GWP of the mixed refrigerant is 250; located further to the right than the line, the GWP of the mixed refrigerant is less than 250. Further, it was judged that, in the 3-component composition diagrams of fig. 2 to 9, when the coordinates (x, y, z) are on the line of the straight line AB, the GWP of the mixed refrigerant was 125; located further to the right than the line, the GWP of the mixed refrigerant is less than 125.
It was determined that the straight line connecting point D and point C is located slightly to the left of the curve connecting the points at which the freezing capacity ratio based on R410A was 80%. Therefore, it is determined that the freezing capacity ratio of the mixed refrigerant based on R410A is 80% or more when the coordinates (x, y, z) are located on the left side of the straight line connecting point D and point C.
The coordinates of the points a, B, A ', B', and a "and B" are determined by obtaining approximate expressions based on the respective points described in the above table. Specifically, the calculations were performed as shown in table 11 (points a and B), table 12 (points a 'and B'), and table 13 (points a "and B").
[ Table 21]
Point A
Point B
[ Table 22]
Point A'
Point B'
[ Table 23]
Point A "
Dot B "
The coordinates of the points C to G are determined by obtaining an approximate expression based on each point described in the above table. Specifically, the calculation was performed as shown in table 14.
[ Table 24]
Point C
Point D
Point E
Point F
Point G
[ Table 25]
Point M
Point W
Point N
Point O
Point P
The coordinates of the points on the curve IJ, the curve JK, and the curve KL are determined by obtaining an approximation formula based on each point described in the above table. Specifically, the calculation was performed as shown in table 15.
[ Table 26]
The coordinates of the points on the curve MW and the curve WM are determined by obtaining an approximation formula based on each point described in the above table. Specifically, the following Table 16(0 mass% < CO)2Concentration of 1.2% by mass or less), Table 17 (1.2% by mass < CO)2Concentration of 4.0 mass% or less) and Table 18(4.0 mass% < CO >2Concentration of 7.0 mass% or less).
[ Table 27]
1.2≥CO2>0
[ Table 28]
4.0≥CO2≥1.2
[ Table 29]
7.0≥CO2≥4.0
The coordinates of the points on the curve NO and the curve OP are determined by obtaining an approximation formula based on each point described in the above table. Specifically, the following Table 19(0 mass% < CO)2Concentration of 1.2 mass% or less), table 20(1.2 mass% CO ≦ CO)2Concentration of 4.0 mass% or less) and Table 21(4.0 mass% < CO >2Concentration of 7.0 mass% or less).
[ Table 30]
1.2≥CO2＞0
[ Table 31]
4.0≥CO2≥1.2
[ Table 32]
7.0≥CO2≥4.0
Description of the symbols
1: sample chamber
2: high speed camera
3: xenon lamp
4: collimating lens
5: collimating lens
6: an annular filter.