CN118179255A - Purifying device of electronic grade pentafluoroethane and purifying process adopting purifying device - Google Patents
Purifying device of electronic grade pentafluoroethane and purifying process adopting purifying device Download PDFInfo
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- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 55
- 239000007789 gas Substances 0.000 claims abstract description 53
- 239000001257 hydrogen Substances 0.000 claims abstract description 50
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 33
- 238000000746 purification Methods 0.000 claims abstract description 33
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000006096 absorbing agent Substances 0.000 claims abstract description 27
- 238000007872 degassing Methods 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 25
- 238000007599 discharging Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000002808 molecular sieve Substances 0.000 claims description 44
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 44
- 239000003054 catalyst Substances 0.000 claims description 30
- 238000004458 analytical method Methods 0.000 claims description 25
- 238000001179 sorption measurement Methods 0.000 claims description 24
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 23
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 22
- 238000005070 sampling Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 7
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000012958 reprocessing Methods 0.000 claims description 3
- 238000012797 qualification Methods 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 238000004064 recycling Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 229910018054 Ni-Cu Inorganic materials 0.000 description 6
- 229910018481 Ni—Cu Inorganic materials 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- -1 helium ion Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of pentafluoroethane purification, and particularly relates to a purification device of electronic grade pentafluoroethane and a purification process adopting the purification device. Comprises a reaction kettle, a pentafluoroethane raw material tank and a hydrogen raw material tank which are respectively connected with the reaction kettle; the discharging pipe of the condenser is connected with the middle tank and the carbon dioxide adsorber in two paths, the non-condensable gas outlet of the condenser is connected with the hydrogen separator, and the top of the hydrogen separator is connected with the reaction kettle; the carbon dioxide absorber is connected with the fluorocarbon absorber, and the fluorocarbon absorber is connected with the No. 1 finished product tank and the feed inlet of the degassing tower in two paths; the degassing tower is connected with a heavy-removal rectifying tower, and the heavy-removal rectifying tower is connected with a No. 2 finished product tank and an intermediate tank in two paths after passing through a cooler; the intermediate tank is connected with a condenser. The purification device and the purification process effectively reduce the process flow, improve the utilization rate of resources, and ensure that the purity of the pentafluoroethane product reaches 99.999 percent, thereby meeting the use requirement of semiconductors.
Description
Technical Field
The invention belongs to the technical field of pentafluoroethane purification, and particularly relates to a purification device of electronic grade pentafluoroethane and a purification process adopting the purification device.
Background
Pentafluoroethane, abbreviated as R125 in commerce, is a widely used fluoroalkane. It is mainly used in refrigerant, foaming agent, fire extinguishing agent, cleaning agent and etching agent.
Wherein, the electron-grade pentafluoroethane has higher requirements on gas purity. Although there is no unified standard for electronic grade pentafluoroethane at present, it is known from semiconductor manufacturers that electronic grade pentafluoroethane cannot contain pentafluoroethane. However, pentafluoroethane and pentafluoroethane have azeotropes, and separation is difficult.
For pentafluoroethane prepared by a tetrachloro method, an extraction method is often adopted in industry to separate pentafluoroethane and pentafluoroethane, but the method cannot thoroughly remove pentafluoroethane, and is difficult to reach the electronic grade standard.
U.S. patent No. 6340781B1 describes a process for the catalytic hydrogenation of pentafluoroethane and pentafluoroethane which, although the separation of pentafluoroethane from pentafluoroethane is achieved, the subject of experimental selection is not technical grade pentafluoroethane and cannot be applied to purification of technical grade pentafluoroethane. And the process described in the patent can only remove fluorocarbon impurities to a level below 1%, and cannot meet the production requirement of electronic grade pentafluoroethane.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the purification device of the electronic grade pentafluoroethane, which is reasonable in arrangement and effectively reduces energy consumption.
The invention also provides a purification process using the method, which improves the resource utilization rate, ensures that the purity of pentafluoroethane reaches 99.999 percent, realizes the removal of pentafluoroethane, and has the content of less than 0.001ppm.
The invention relates to a purifying device of electronic grade pentafluoroethane, which comprises a pentafluoroethane raw material tank, a hydrogen raw material tank, a reaction kettle, a condenser, a middle tank, a hydrogen separator, a carbon dioxide adsorber, a fluorocarbon adsorber, a degasser, a heavy removal rectifying tower, a cooler, a No. 1 finished product tank and a No. 2 finished product tank, wherein the pentafluoroethane raw material tank and the hydrogen raw material tank are respectively connected with two feed inlets of the reaction kettle; the discharging pipe of the condenser is divided into two paths, one path is connected with the feeding hole of the middle tank, the other path is connected with the feeding hole of the carbon dioxide adsorber, the non-condensable gas exhaust port of the condenser is connected with the feeding hole of the hydrogen separator, and the discharging pipe at the top of the hydrogen separator is connected with the feeding hole of the reaction kettle; the discharging port of the carbon dioxide absorber is connected with the feeding port of the fluorocarbon absorber, the discharging pipe of the fluorocarbon absorber is divided into two paths, one path is connected with the No. 1 finished product tank, and the other path is connected with the feeding port of the degassing tower; the bottom of the degassing tower is connected with a feeding pipe of the heavy-duty stripping and rectifying tower, a discharging pipe of the heavy-duty stripping and rectifying tower is divided into two paths after passing through a cooler, one path of the discharging pipe is connected with a No. 2 finished product tank, and the other path of the discharging pipe is connected with a feeding port of the intermediate tank; the discharge pipe of the middle tank is connected with the feed inlet of the condenser.
And each pipeline of the purification device is provided with a pump and a valve according to actual operation requirements so as to realize the conveying of materials among all the devices and control the flow direction of the materials.
The condenser has the functions of removing impurities such as oxygen, nitrogen and the like in pentafluoroethane and partial non-condensable gas with higher boiling point, effectively prolonging the service time of the subsequent adsorbent and improving the separation quality of the subsequent degassing tower. And secondly, recycling unreacted hydrogen, and reducing resource loss.
The hydrogen separator is used for separating hydrogen from other noncondensable gases and recycling the hydrogen.
The intermediate tank not only can be used as the discharging and storing device of the condensation separator, but also can store the subsequent unqualified products back, and the recycling treatment is performed again, so that the waste is reduced, and the recycling is realized.
The two-stage adsorption device is adopted after the condenser and is mainly used for removing carbon dioxide, water, difluoromethane, trifluoromethane, trifluoro-chloromethane and trifluoroethane in pentafluoroethane. Each adsorber is provided with a jacket, and circulating water can be introduced to control the adsorption temperature and take away the adsorption heat, so that the sintering of the adsorbent and the explosion of the device caused by the adsorption heat release are prevented.
The degasser and the rectifying tower play a role in rectifying and separating, impurities in pentafluoroethane are further removed, if the quality of the rectified product is qualified, the product is directly filled into a No. 2 finished product tank, and if the product is unqualified, the product is returned to the intermediate tank for recycling treatment so as to meet the use requirements of downstream manufacturers.
The purification device is provided with detection pipes at the discharge inlets of the adsorbers and the rectifying towers, so that the materials processed by the equipment are analyzed, if the materials are qualified, the materials can be directly fed into a finished product tank, and if the materials are unqualified, the next treatment is continued or the materials are returned to the front end for reprocessing.
The purification process of the purification device adopting electronic grade pentafluoroethane provided by the invention comprises the following steps:
A. catalytic hydrogenation: firstly, starting a vacuum pump to enable the whole device to be in a vacuum state, then, closing the vacuum pump, introducing pentafluoroethane to be purified and hydrogen into a reaction kettle, reacting under the catalysis of a Ni-Cu-Ce/gamma-Al 2O3 catalyst, sampling and detecting gas of the reaction kettle, and introducing the qualified gas into a condenser;
B. Cooling and separating: introducing the gas after the catalytic hydrogenation reaction into a condenser for cooling, and opening a vacuum pump to pump out non-condensable gas and send the non-condensable gas to a hydrogen separator after cooling; closing a vacuum pump, taking condensate at a discharge port of a condenser for analysis, introducing the condensate into a carbon dioxide adsorber after the condensate is qualified, discharging the condensate into a middle tank if the condensate is unqualified, and introducing the condensate into the condenser again for cooling separation until the condensate is qualified;
C. Adsorption: introducing the gas adsorbed by the carbon dioxide adsorber into a fluorocarbon adsorber with a modified 4A molecular sieve for adsorption, sampling and analyzing at a discharge port of the fluorocarbon adsorber, and introducing the gas into a 1# finished product tank if the product is qualified to obtain electronic grade pentafluoroethane; if the product is unqualified, introducing the product into a degassing tower for rectification;
D. degassing: sampling and analyzing at a discharge port of the degassing tower, and if the product is qualified, introducing the product into a No. 1 finished product tank to obtain electronic grade pentafluoroethane; if the product is unqualified, feeding the product into a heavy-duty removal rectifying tower for rectifying;
E. and (3) removing heavy and rectifying: sampling and analyzing at a discharge port of the heavy-removal rectifying tower, and if the product is qualified, introducing the product into a No. 2 finished product tank to obtain electronic grade pentafluoroethane; if the product is unqualified, the product is fed into a middle tank for reprocessing;
F. Hydrogen recovery: and separating the non-condensable gas which is introduced into the hydrogen separator, and recovering hydrogen.
The index of the pentafluoroethane to be purified is ：O2＜500ppm,N2＜500ppm,CO2＜1500ppm,CH4＜5ppm,CF3CF3＜5ppm,CH2FCH3＜1ppm,CClF3＜5ppm,CHF3＜20ppm,CH2F2＜50ppm,CF3CClF2＜300ppm,H2O＜1ppm.
The index of the electronic grade pentafluoroethane is ：O2＜1ppm,N2＜1ppm,CO2＜1ppm,CH4＜1ppm,CF3CClF2＜0.001ppm,, the total amount of all fluorocarbons is less than 1ppm, and CHF 2CF3 is more than 99.999 percent.
The reaction temperature of the reaction in the step A is 200-400 ℃, the reaction pressure is 150-300 kPa, and the molar ratio of hydrogen to pentafluoroethane material is (1-3): 1; the temperature of the condenser in the step B is-55 ℃ to-40 ℃ and the pressure is 0.4-0.85 MPa; the working temperature of the carbon dioxide absorber and the fluorocarbon absorber in the step C is 20-70 ℃; the pressure of the degassing tower in the step D is 1.5-3.5 MPa, and the temperature is controlled to be 20-25 ℃; and E, controlling the pressure of the heavy component removal rectifying tower to be 1.5-3 MPa and controlling the temperature to be 15-20 ℃.
The carbon dioxide adsorber is filled with CaO and NaOH for removal of CO 2 and H 2 O produced after the hydrogenation reaction. The fluorocarbon adsorber is equipped with a modified 4A molecular sieve for removal of various fluorocarbon impurities.
The preparation method of the Ni-Cu-Ce/gamma-Al 2O3 catalyst comprises the following steps:
1) Adding Ni (NO 3)2、Cu(NO3)2、Ce(NO3)3 and stirring to 200mL of water to obtain Ni-Cu-Ce solution;
2) Adding 100mL of pure water and 5mol of gamma-Al 2O3, stirring for 12 hours, loading, and evaporating in a water bath at 90 ℃;
3) Roasting in a muffle furnace at 300-400 ℃ for 4-8 hours after drying; cooling to obtain a Ni-Cu-Ce/gamma-Al 2O3 catalyst;
Preferably, the molar ratio of Ni (NO 3)2、Cu(NO3)2、Ce(NO3)3) is (1-10): 1.
The index of the qualified gas in the step A is as follows: CF 3CClF2 < 0.001ppm; and B, the qualification index of the condensate liquid is as follows: o 2＜1ppm,N2＜1ppm,CO2＜500ppm,CH4＜1ppm,H2 < 1ppm.
The preparation method of the modified 4A molecular sieve in the step C comprises the following steps:
a) Adding 50mL of 1mol/L polyethylenimine and 50mL of 1mol/L ammonia water into 200mL of water, and uniformly stirring to obtain a solution;
b) Soaking the 4A molecular sieve into the solution, stirring for 30min, and washing the molecular sieve;
c) Then, the molecular sieve was immersed in a 500mL mixed solution containing 4mol of CaCl 2 and 1mol of Ce (NO 3)3;
d) Pretreating the soaked 4A molecular sieve for 1-3 hours at 60-80 ℃, then treating for 8-12 hours at 150-180 ℃, and cooling to obtain the modified 4A molecular sieve.
The mol ratio of CaCl 2、Ce(NO3)3 is (0.2-5): 1.
Compared with the prior art, the invention has the following beneficial effects:
1. The invention utilizes hydrogenation reaction to realize complete removal of pentafluoroethane in industrial grade pentafluoroethane, solves the problem that the traditional extraction process can not completely separate pentafluoroethane and pentafluoroethane, and can control the impurity in pentafluoroethane to be below 0.001% by the process combining condensation, catalytic hydrogenation, adsorption and rectification to stably produce electronic grade pentafluoroethane. The process flow is circularly carried out, so that the process flow is effectively reduced, the energy consumption is reduced, and the purity of the pentafluoroethane product reaches 99.999 percent.
2. The special hydrogenation catalyst is used in the catalytic hydrogenation reaction, the electron transfer rate and the hydrogenation reaction rate can be effectively improved by the bimetal synergistic effect of Ni and Cu, the specific surface area of the catalyst is effectively increased by introducing rare earth metal element Ce into the catalyst, the dispersity of Ni and Cu on a carrier is improved, and the reactivity, selectivity and stability of the hydrogenation reaction can be further improved.
3. Compared with the traditional molecular sieve, the modified 4A molecular sieve used in the fluorocarbon adsorber increases more adsorption sites, and in addition, the introduction of Ca 2+、Ce3+ can form a complex with adsorbed impurities, so that the modified 4A molecular sieve has stronger adsorption capacity and longer service life.
Drawings
FIG. 1 is a schematic diagram of the purification apparatus of electronic grade pentafluoroethane of the present invention;
In the figure: 1. a hydrogen gas raw material tank; 2. pentafluoroethane raw material tank; 3. a reaction kettle; 4. a condenser; 5. an intermediate tank; 6. a hydrogen separator; 7. a carbon dioxide adsorber; 8. a fluorocarbon adsorber; 9. a degasser; 10. a heavy-removal rectifying tower; 11. a cooler; 12. a No. 1 finished product tank; 13. 2# finished tank.
Detailed Description
The invention is further illustrated by the following examples.
The 4A molecular sieves used in the examples and comparative examples were purchased from Michael reagent company.
The analytical instrument of pentafluoroethane in the examples included helium ion gas chromatograph for measuring noncondensable gas and fluorocarbon content and moisture meter for measuring moisture.
Example 1
As shown in fig. 1, the purification device of electronic grade pentafluoroethane comprises a pentafluoroethane raw material tank 2, a hydrogen raw material tank 1, a reaction kettle 3, a condenser 4, an intermediate tank 5, a hydrogen separator 6, a carbon dioxide adsorber 7, a fluorocarbon adsorber 8, a degassing tower 9, a heavy removal rectifying tower 10, a cooler 11, a 1# finished product tank 12 and a 2# finished product tank 13, wherein the pentafluoroethane raw material tank 2 and the hydrogen raw material tank 1 are respectively connected with two feed inlets of the reaction kettle 3; the discharging pipe of the condenser 4 is divided into two paths, one path is connected with the feeding port of the intermediate tank 5, the other path is connected with the feeding port of the carbon dioxide adsorber 7, the non-condensable gas exhaust port of the condenser 4 is connected with the feeding port of the hydrogen separator 6, and the discharging pipe at the top of the hydrogen separator 6 is connected with the feeding port of the reaction kettle 3; the discharge port of the carbon dioxide absorber 7 is connected with the feed port of the fluorocarbon absorber 8, the discharge pipe of the fluorocarbon absorber 8 is divided into two paths, one path is connected with the No. 1 finished product tank 12, and the other path is connected with the feed port of the degassing tower 9; the bottom of the degassing tower 9 is connected with a feeding pipe of a heavy removal rectifying tower 10, a discharging pipe of the heavy removal rectifying tower 10 is divided into two paths after passing through a cooler 11, one path is connected with a No. 2 finished product tank 13, and the other path is connected with a feeding port of the intermediate tank 5; the discharge pipe of the intermediate tank 5 is connected with the feed inlet of the condenser 4.
The condenser 4 has the function of removing impurities such as oxygen, nitrogen and the like in pentafluoroethane and partial non-condensable gas with higher boiling point, so that the service time of a subsequent adsorbent can be effectively prolonged, and the separation quality of a subsequent degassing tower 9 can be improved. And secondly, recycling unreacted hydrogen, and reducing resource loss.
The intermediate tank 5 not only can be used as the discharging and storing device of the condensation separator, but also can store the subsequent unqualified products back, and the recycling treatment is performed again, so that the waste is reduced, and the recycling is realized.
The two-stage adsorption device is adopted after the condenser 4 and is mainly used for removing carbon dioxide, water, difluoromethane, trifluoromethane, trifluoro-chloromethane and trifluoroethane in pentafluoroethane. Each adsorber is provided with a jacket, and circulating water can be introduced to control the adsorption temperature and take away the adsorption heat, so that the sintering of the adsorbent and the explosion of the device caused by the adsorption heat release are prevented.
The degassing tower 9 and the heavy-duty rectification tower 10 play a role in rectification separation, impurities in pentafluoroethane are further removed, if the quality of the rectified product is qualified, the product is directly filled into a No. 2 finished product tank, and if the product is unqualified, the product is returned to the intermediate tank 5 for recycling treatment so as to meet the use requirements of downstream factories.
Example 2
The pentafluoroethane was purified using the purification apparatus in example 1:
Through analysis and detection, the content of each impurity of pentafluoroethane to be purified is ：O2：436.431ppm,N2：457.260ppm,CO2：1245.631ppm,CH4：3.896ppm,CF3CF3：1.432ppm,CH2FCH3：0.003ppm,CClF3：4.216ppm,CHF3：17.832ppm,CH2F2：45.967ppm,CF3CClF2：255.861ppm,H2O：0.431ppm.
The index of the electronic grade pentafluoroethane is ：O2＜1ppm,N2＜1ppm,CO2＜1ppm,CH4＜1ppm,CF3CClF2＜0.001ppm,, the total amount of all fluorocarbons is less than 1ppm, and CHF 2CF3 is more than 99.999 percent.
The purification process comprises the following steps:
A. Catalytic hydrogenation: firstly, starting a vacuum pump, when the vacuum degree of the whole device is lower than 10Pa, closing the vacuum pump, introducing raw materials to be purified into a reaction kettle 3, reacting under the catalysis of a Ni-Cu-Ce/gamma-Al 2O3 catalyst according to the molar ratio of 1:2, controlling the reaction temperature to be 300 ℃, controlling the reaction pressure to be 200kPa, sampling and detecting the gas of the reaction kettle 3 every 1h, and after 5h, enabling the gas chromatography to not detect pentafluoroethane (namely, the pentafluoroethane content is less than 0.001 ppm), and introducing the gas into a condenser 4;
B. Cooling and separating: introducing the gas after the catalytic hydrogenation reaction into a condenser 4 for cooling, controlling the temperature of the condenser 4 at minus 50+/-1 ℃, controlling the pressure of the condenser to be about 0.6+/-0.02 MPa, when the liquid level of the condenser reaches 2/3, opening a vacuum pump to pump non-condensable gas to a hydrogen separator 6, closing the vacuum pump, taking condensate at a discharge hole of the condenser 4 for analysis, and introducing the gas into a carbon dioxide adsorber 7 according to the sample analysis result O2：0.763ppm,N2：0.832ppm,CO2：456.532ppm,CH4：0.443ppm,H2：0.564ppm, reaching the index requirement;
C. Adsorption: and (3) introducing the cooled and separated qualified condensate into a carbon dioxide absorber 7 filled with CaO and NaOH (molar ratio is 3:1) and a fluorocarbon absorber 8 filled with a modified 4A molecular sieve in sequence at a flow rate of 30L/min for adsorption, controlling the temperature at 40+/-1 ℃, carrying out sampling analysis at the outlet of the carbon dioxide absorber 7, carrying out sampling analysis at the discharge port of the fluorocarbon absorber 8, wherein the carbon dioxide content is 0.532ppm, and discharging the result that O2：0.784ppm,N2：0.857ppm,CO2：0.371ppm,CH4：0.242ppm,CF3CF3：0.560ppm,CHF3：0.016ppm,CH2F2：0.033ppm,H2O：0.078ppm, and other impurities are 0.CF3CF3+CHF3+CH2F2=0.609ppm,CHF2CF3＞99.999%, according with electronic grade standards into a No.1 finished product tank 12.
D. Hydrogen recovery: the non-condensable gas introduced into the hydrogen separator 6 is separated, and hydrogen is recovered.
The preparation method of the Ni-Cu-Ce/gamma-Al 2O3 catalyst comprises the following steps:
1) To 200mL of water was added 2mol of Ni (NO 3)2, 1mol of Cu (NO 3)2, 0.2mol of Ce (NO 3)3, stirring to give a Ni-Cu-Ce solution;
2) Adding 100mL of pure water and 5mol of gamma-Al 2O3 into the Ni-Cu-Ce solution, loading for 12 hours, and drying at 60 ℃;
3) Baking in a muffle furnace at 350 ℃ for 6 hours after drying; cooling to obtain a Ni-Cu-Ce/gamma-Al 2O3 catalyst;
the preparation method of the modified 4A molecular sieve comprises the following steps:
a) Adding 50mL of 1mol/L polyethylenimine and 50mL of 1mol/L ammonia water into 200mL of water, and uniformly stirring;
b) Soaking the 4A molecular sieve into the solution, stirring for 6 hours, and washing the molecular sieve;
c) Then, the molecular sieve is soaked in 500mL mixed solution containing 4mol of CaCl 2 and 1mol of Ce (NO 3)3 for 8 hours;
d) Pretreating the soaked 4A molecular sieve for 2 hours at 70 ℃, then treating for 10 hours at 160 ℃, and cooling to obtain the modified 4A molecular sieve.
Example 3
The pentafluoroethane was purified using the purification apparatus in example 1:
through analysis and detection, the content of each impurity of pentafluoroethane to be purified is ：O2：426.764ppm,N2：445.712ppm,CO2：1362.325ppm,CH4：4.974ppm,CF3CF3：4.524ppm,CH2FCH3：0.010ppm,CClF3：4.832ppm,CHF3：18.112ppm,CH2F2：48.457ppm,CF3CClF2：261.732ppm,H2O：0.425ppm.
The index of the electronic grade pentafluoroethane is ：O2＜1ppm,N2＜1ppm,CO2＜1ppm,CH4＜1ppm,CF3CClF2＜0.001ppm,, the total amount of all fluorocarbons is less than 1ppm, and CHF 2CF3 is more than 99.999 percent.
A. catalytic hydrogenation: firstly, starting a vacuum pump, when the vacuum degree of the whole device is lower than 10Pa, closing the vacuum pump, introducing raw materials to be purified into a reaction kettle 3, reacting under the catalysis of a Ni-Cu-Ce/gamma-Al 2O3 catalyst according to the molar ratio of 1:1, controlling the reaction temperature to be 200 ℃, controlling the reaction pressure to be 150kPa, sampling and detecting the gas of the reaction kettle 3 every 1h, and after 8h, enabling the gas chromatography to not detect pentafluoroethane (namely, the pentafluoroethane content is less than 0.001 ppm), and introducing the gas into a condenser 4;
B. Cooling and separating: introducing the gas after the catalytic hydrogenation reaction into a condenser 4 for cooling, controlling the temperature of the condenser 4 at-55+/-1 ℃, controlling the pressure of the condenser at 0.4+/-0.02 MPa, when the liquid level of the condenser reaches 2/3, starting a vacuum pump to pump out non-condensable gas, delivering the non-condensable gas to a hydrogen separator 6, closing the vacuum pump, taking condensate at a discharge port of the condenser 4 for analysis, and introducing the gas into a carbon dioxide adsorber 7 according to the sample analysis result O2：0.752ppm,N2：0.814ppm,CO2：471.124ppm,CH4：0.462ppm,H2：0.561ppm, reaching the index requirement;
C. Adsorption: and (3) introducing the cooled and separated qualified condensate into a carbon dioxide absorber 7 filled with CaO and NaOH (the molar ratio is 3:1) and a fluorocarbon absorber 8 filled with a modified 4A molecular sieve in sequence at a flow rate of 30L/min for adsorption, controlling the temperature to be 20+/-1 ℃, carrying out sampling analysis at the outlet of the carbon dioxide absorber 7, wherein the carbon dioxide content is 0.455ppm, and carrying out sampling analysis at the discharge port of the fluorocarbon absorber 8, wherein the analysis result is O2：0.753ppm,N2：0.815ppm,CO2：0.386ppm,CH4：0.113ppm,CF3CF3：2.230ppm,CHF3：0.009ppm,CH2F2：0.041ppm,H2O：0.078ppm, and the content of other impurities is 0.CF 3CF3+CHF3+CH2F2 = 2.280ppm, which does not meet the electronic grade standards, is discharged into the degassing column 9.
D. Degassing: and (3) introducing the unqualified gas after adsorption into a degassing tower 9, controlling the temperature to be 22+/-1 ℃, controlling the pressure to be 2+/-0.02 MPa, sampling and analyzing at a discharge hole of the degassing tower 9, wherein the analysis result shows that the content of other impurities O2：0.236ppm,N2：0.251ppm,CO2：0.213ppm,CH4：0.099ppm,CF3CF3：0.430ppm,CHF3：0.008ppm,CH2F2：0.040ppm,H2O：0.078ppm, is 0.CF3CF3+CHF3+CH2F2=0.478ppm,CHF2CF3＞99.999%, and meets the electronic grade standard, and discharging the unqualified gas into a No. 1 finished product tank 12.
E. Hydrogen recovery: the non-condensable gas introduced into the hydrogen separator 6 is separated, and hydrogen is recovered.
The preparation method of the Ni-Cu-Ce/gamma-Al 2O3 catalyst comprises the following steps:
1) To 200mL of water, 1.5mol of Ni (NO 3)2, 2mol of Cu (NO 3)2, 0.2mol of Ce (NO 3)3, stirring) was added to obtain a Ni-Cu-Ce solution;
2) Adding 100mL of pure water and 5mol of gamma-Al 2O3 into the Ni-Cu-Ce solution, loading for 12 hours, and drying at 60 ℃;
3) Baking in a muffle furnace at 300 ℃ for 8 hours after drying; cooling to obtain a Ni-Cu-Ce/gamma-Al 2O3 catalyst;
the preparation method of the modified 4A molecular sieve comprises the following steps:
a) Adding 50mL of 1mol/L polyethylenimine and 50mL of 1mol/L ammonia water into 200mL of water, and uniformly stirring;
b) Soaking the 4A molecular sieve into the solution, stirring for 6 hours, and washing the molecular sieve;
c) Then, the molecular sieve is soaked in 500mL mixed solution containing 5mol of CaCl 2 and 1mol of Ce (NO 3)3 for 8 hours;
d) Pretreating the soaked 4A molecular sieve for 3 hours at 60 ℃, then treating for 12 hours at 150 ℃, and cooling to obtain the modified 4A molecular sieve.
Example 4
The pentafluoroethane was purified using the purification apparatus in example 1:
Through analysis and detection, the content of each impurity of pentafluoroethane to be purified is ：O2：431.311ppm,N2：444.447ppm,CO2：1311.627ppm,CH4：3.841ppm,CF3CF3：4.336ppm,CH2FCH3：0.750ppm,CClF3：4.654ppm,CHF3：18.213ppm,CH2F2：48.346ppm,CF3CClF2：262.111ppm,H2O：0.416ppm.
The index of the electronic grade pentafluoroethane is ：O2＜1ppm,N2＜1ppm,CO2＜1ppm,CH4＜1ppm,CF3CClF2＜0.001ppm,, the total amount of all fluorocarbons is less than 1ppm, and CHF 2CF3 is more than 99.999 percent.
A. catalytic hydrogenation: firstly, starting a vacuum pump, when the vacuum degree of the whole device is lower than 10Pa, closing the vacuum pump, introducing raw materials to be purified into a reaction kettle 3, reacting under the catalysis of a Ni-Cu-Ce/gamma-Al 2O3 catalyst according to the molar ratio of 1:3, controlling the reaction temperature to be 400 ℃, controlling the reaction pressure to be 300kPa, sampling and detecting the gas of the reaction kettle 3 every 1h, and after 7h, enabling the gas chromatography to not detect pentafluoroethane (namely, the pentafluoroethane content is less than 0.001 ppm), and introducing the gas into a condenser 4;
B. Cooling and separating: introducing the gas after the catalytic hydrogenation reaction into a condenser 4 for cooling, controlling the temperature of the condenser 4 at minus 40+/-1 ℃, controlling the pressure of the condenser to be about 0.85+/-0.02 MPa, when the liquid level of the condenser reaches 2/3, opening a vacuum pump to pump out non-condensable gas, delivering the non-condensable gas to a hydrogen separator 6, closing the vacuum pump, taking condensate at a discharge hole of the condenser 4 for analysis, and introducing the gas into a carbon dioxide adsorber 7 according to a sample analysis result O2：0.836pm,N2：0.853ppm,CO2：493.654ppm,CH4：0.495ppm,H2：0.589ppm, reaching the index requirement;
C. Adsorption: and (3) introducing the cooled and separated qualified condensate into a carbon dioxide absorber 7 filled with CaO and NaOH (the molar ratio is 3:1) and a fluorocarbon absorber 8 filled with a modified 4A molecular sieve in sequence at a flow rate of 30L/min for adsorption, controlling the temperature at 70+/-1 ℃, carrying out sampling analysis at the outlet of the carbon dioxide absorber 7, wherein the carbon dioxide content is 0.697ppm, and carrying out sampling analysis at the discharge port of the fluorocarbon absorber 8, wherein the analysis result is O2：0.806ppm,N2：0.833ppm,CO2：0.411ppm,CH4：0.154ppm,CF3CF3：2.211ppm,CH2FCH3：0.650ppm,CHF3：0.110ppm,CH2F2：0.095ppm,H2O：0.068ppm, and the content of other impurities is 0.CF 3CF3+CH2FCH3+CHF3+CH2F2 = 3.066pm, which does not meet electronic grade standards, is discharged into degasser 9.
D. Degassing: and (3) introducing the unqualified gas after adsorption into a degassing tower 9, controlling the temperature to be 22+/-1 ℃, controlling the pressure to be 2+/-0.02 MPa, and carrying out sampling analysis on a discharge hole of the degassing tower 9, wherein the analysis result is O2：0.263ppm,N2：0.301ppm,CO2：0.222ppm,CH4：0.081ppm,CF3CF3：0.436ppm,CH2FCH3：0.538ppm,CHF3：0.013ppm,CH2F2：0.036ppm,H2O：0.077ppm, and the content of other impurities is 0.CF 3CF3+CH2FCH3+CHF3+CH2F2 =1.023 ppm, which does not meet the electronic grade standard, is fed to the de-heavy rectifying column 10.
E. Weight removal: and introducing the degassed unqualified liquid into a heavy-duty stripping and rectifying tower 10, controlling the temperature to be 17+/-1 ℃, controlling the pressure to be 2+/-0.02 MPa, sampling and analyzing a discharge hole of the heavy-duty stripping and rectifying tower 10, wherein the analysis result shows that the content of other impurities is O2：0.261ppm,N2：0.299ppm,CO2：0.223ppm,CH4：0.075ppm,CF3CF3：0.431ppm,CH2FCH3：0.104ppm,CHF3：0.009ppm,CH2F2：0.033ppm,H2O：0.078ppm, and 0.CF3CF3+CH2FCH3+CHF3+CH2F2=0.577ppm,CHF2CF3＞99.999%, meets the electronic grade standard, cooling the liquid by a cooler 11, and discharging the cooled liquid into a No. 2 finished product tank 13.
F. Hydrogen recovery: the non-condensable gas introduced into the hydrogen separator 6 is separated, and hydrogen is recovered.
The preparation method of the Ni-Cu-Ce/gamma-Al 2O3 catalyst comprises the following steps:
1) To 200mL of water, 0.2mol of Ni (NO 3)2, 0.2mol of Cu (NO 3)2, 0.2mol of Ce (NO 3)3, stirring) was added to obtain a Ni-Cu-Ce solution;
2) Adding 100mL of pure water and 5mol of gamma-Al 2O3 into the Ni-Cu-Ce solution, loading for 12 hours, and drying at 60 ℃;
3) Baking in a muffle furnace at 400 ℃ for 4 hours after drying; cooling to obtain a Ni-Cu-Ce/gamma-Al 2O3 catalyst;
the preparation method of the modified 4A molecular sieve comprises the following steps:
a) Adding 50mL of 1mol/L polyethylenimine and 50mL of 1mol/L ammonia water into 200mL of water, and uniformly stirring;
b) Soaking the 4A molecular sieve into the solution, stirring for 6 hours, and washing the molecular sieve;
c) Then, the molecular sieve is soaked in 500mL mixed solution containing 1mol of CaCl 2 and 5mol of Ce (NO 3)3 for 8 hours;
d) Pretreating the soaked 4A molecular sieve for 1h at 80 ℃, then treating for 8h at 180 ℃, and cooling to obtain the modified 4A molecular sieve.
Comparative example 1
The other conditions of example 2 were kept unchanged, and only the hydrogenation catalyst was replaced with a conventional Ni/gamma-Al 2O3 catalyst.
A. Catalytic hydrogenation: the vacuum pump is started first, and then the vacuum pump is closed when the vacuum degree of the device is lower than 10 Pa. The raw materials of pentafluoroethane and hydrogen are introduced into a reaction kettle 3 filled with a Ni/gamma-Al 2O3 catalyst according to the mol ratio of 1:2 for reaction, the reaction temperature is controlled to be 400 ℃, the reaction pressure is 200kPa, the gas of the reaction kettle 3 is sampled and detected every 1h, and after 24h, the content of pentafluoroethane by gas chromatography is 4.76ppm, so that the pentafluoroethane cannot be completely removed.
The preparation method of the Ni/gamma-Al 2O3 catalyst comprises the following steps:
The preparation method of the Ni/gamma-Al 2O3 catalyst comprises the following steps:
1) 3.2mol of Ni (NO 3)2 was added to 200mL of water and stirred to obtain a Ni solution;
2) Adding 100mL of pure water and 5mol of gamma-Al 2O3 into the Ni solution for loading for 12 hours, and then drying at 60 ℃;
3) Baking in a muffle furnace at 350 ℃ for 6 hours after drying; cooling to obtain a Ni/gamma-Al 2O3 catalyst;
Comparative example 2
The other conditions of example 2 were kept unchanged, and only the hydrogenation catalyst was replaced with a Ni-Cu/gamma-Al 2O3 catalyst.
A. Catalytic hydrogenation: the vacuum pump is started first, and then the vacuum pump is closed when the vacuum degree of the device is lower than 10 Pa. The raw materials of pentafluoroethane and hydrogen are introduced into a reaction kettle 3 filled with a Ni-Cu/gamma-Al 2O3 catalyst according to the mol ratio of 1:2 for reaction, the reaction temperature is controlled to be 400 ℃, the reaction pressure is controlled to be 200kPa, the gas of the reaction kettle 3 is sampled and detected every 1h, and after 24h, the content of pentafluoroethane by gas chromatography is 1.31ppm, so that the pentafluoroethane cannot be thoroughly removed.
The preparation method of the Ni-Cu/gamma-Al 2O3 catalyst comprises the following steps:
1) 2.1mol of Ni (NO 3)2, 1.1mol of Cu (NO 3)2, stirring) was added to 200mL of water to obtain a Ni-Cu solution;
2) Adding 100mL of pure water and 5mol of gamma-Al 2O3 into the Ni-Cu solution, loading for 12 hours, and drying at 60 ℃;
3) Baking in a muffle furnace at 350 ℃ for 6 hours after drying; cooling to obtain a Ni-Cu/gamma-Al 2O3 catalyst;
Comparative example 3
The other conditions of example 2 were kept unchanged, and only the adsorbent of the fluorocarbon adsorber was replaced with a common 4A molecular sieve. Sampling analysis is carried out at the outlet of the fluorocarbon adsorber, and the analysis result is O2：0.724ppm,N2：0.831ppm,CO2：0.742ppm,CH4：0.574ppm,CF3CF3：0.520ppm,CHF3：1.732ppm,CH2F2：2.614ppm,H2O：0.124ppm, that the content of other impurities is 0.CF 3CF3+CHF3+CH2F2 = 4.866ppm, which does not meet the electronic-grade standard.
It can be seen from examples 2-4 that the process was successful in producing electronic grade pentafluoroethane with the selective hydrogenation catalyst being Ni-Cu-Ce/gamma-Al 2O3 and the fluorocarbon adsorber adsorbent being a modified 4A molecular sieve.
It can be seen from the combination of comparative example 1 and comparative example 2 that the prepared Ni-Cu-Ce/gamma-Al 2O3 can significantly promote the progress of hydrogenation reaction. Comparative example 1 illustrates that the synergistic effect of the bimetal has a certain positive significance for the reaction; comparative example 2 illustrates that the introduction of the rare earth element Ce greatly accelerates the reaction process.
Comparative example 3 shows that the modified 4A molecular sieve has stronger adsorption performance than the common molecular sieve.
Claims (10)
1. The purifying device of the electronic grade pentafluoroethane is characterized by comprising a pentafluoroethane raw material tank (2), a hydrogen raw material tank (1), a reaction kettle (3), a condenser (4), an intermediate tank (5), a hydrogen separator (6), a carbon dioxide adsorber (7), a fluorocarbon adsorber (8), a degassing tower (9), a heavy removal rectifying tower (10), a cooler (11), a No. 1 finished product tank (12) and a No. 2 finished product tank (13), wherein the pentafluoroethane raw material tank (2) and the hydrogen raw material tank (1) are respectively connected with two feed inlets of the reaction kettle (3); the discharging pipe of the condenser (4) is divided into two paths, one path is connected with the feeding hole of the intermediate tank (5), the other path is connected with the feeding hole of the carbon dioxide absorber (7), the non-condensable gas exhaust hole of the condenser (4) is connected with the feeding hole of the hydrogen separator (6), and the discharging pipe at the top of the hydrogen separator (6) is connected with the feeding hole of the reaction kettle (3); the discharge port of the carbon dioxide absorber (7) is connected with the feed port of the fluorocarbon absorber (8), the discharge pipe of the fluorocarbon absorber (8) is divided into two paths, one path is connected with the No. 1 finished product tank (12), and the other path is connected with the feed port of the degassing tower (9); the bottom of the degassing tower (9) is connected with a feed pipe of the heavy removal rectifying tower (10), a discharge pipe of the heavy removal rectifying tower (10) is divided into two paths after passing through a cooler (11), one path is connected with a No. 2 finished product tank (13), and the other path is connected with a feed inlet of the intermediate tank (5); the discharging pipe of the middle tank (5) is connected with the feeding port of the condenser (4).
2. A purification process employing the purification apparatus for electronic grade pentafluoroethane as claimed in claim 1, characterized by comprising the steps of:
A. Catalytic hydrogenation: firstly, starting a vacuum pump to enable the whole device to be in a vacuum state, then, closing the vacuum pump, introducing pentafluoroethane and hydrogen to be purified into a reaction kettle (3), reacting under the catalysis of a Ni-Cu-Ce/gamma-Al 2O3 catalyst, sampling and detecting the gas of the reaction kettle (3), and introducing the qualified gas into a condenser (4);
B. Cooling and separating: introducing the gas after the catalytic hydrogenation reaction into a condenser (4) for cooling, and opening a vacuum pump to pump out non-condensable gas and send the non-condensable gas to a hydrogen separator (6) after cooling; closing a vacuum pump, taking condensate at a discharge port of a condenser (4) for analysis, introducing the condensate into a carbon dioxide adsorber (7) after the condensate is qualified, discharging the condensate into a middle tank (5) if the condensate is unqualified, and introducing the condensate into the condenser (4) again for cooling and separating until the condensate is qualified;
C. Adsorption: introducing the gas adsorbed by the carbon dioxide adsorber (7) into a fluorocarbon adsorber (8) provided with a modified 4A molecular sieve for adsorption, sampling and analyzing at a discharge port of the fluorocarbon adsorber (8), and introducing the gas into a 1# finished product tank (12) if the product is qualified to obtain electronic grade pentafluoroethane; if the product is unqualified, feeding the product into a degassing tower (9) for rectification;
D. degassing: sampling and analyzing at a discharge hole of a degassing tower (9), and if the product is qualified, introducing the product into a No. 1 finished product tank (12) to obtain electronic grade pentafluoroethane; if the product is unqualified, feeding the product into a heavy-duty removal rectifying tower (10) for rectifying;
E. And (3) removing heavy and rectifying: sampling and analyzing a discharge hole of the heavy-duty removal rectifying tower (10), and if the product is qualified, introducing the product into a No.2 finished product tank (13) to obtain electronic grade pentafluoroethane; if the product is unqualified, the product is fed into a middle tank (5) for reprocessing;
F. Hydrogen recovery: separating the noncondensable gas introduced into the hydrogen separator (6) to recover hydrogen;
The index of the electronic grade pentafluoroethane is ：O2＜1ppm,N2＜1ppm,CO2＜1ppm,CH4＜1ppm,CF3CClF2＜0.001ppm,, the total amount of all fluorocarbons is less than 1ppm, and CHF 2CF3 is more than 99.999%;
The index of the qualified gas in the step A is as follows: CF 3CClF2 < 0.001ppm; and B, the qualification index of the condensate liquid is as follows: o 2＜1ppm,N2＜1ppm,CO2＜500ppm,CH4＜1ppm,H2 < 1ppm.
3. The purification process according to claim 2, wherein the index of pentafluoroethane to be purified is ：O2＜500ppm,N2＜500ppm,CO2＜1500ppm,CH4＜5ppm,CF3CF3＜5ppm,CH2FCH3＜1ppm,CClF3＜5ppm,CHF3＜20ppm,CH2F2＜50ppm,CF3CClF2＜300ppm,H2O＜1ppm.
4. The purification process according to claim 2, wherein the reaction temperature in the step A is 200-400 ℃, the reaction pressure is 150-300 kPa, and the molar ratio of hydrogen to pentafluoroethane is (1-3): 1.
5. The purification process according to claim 2, wherein the condenser (4) in step B has a temperature of-55 ℃ to-40 ℃ and a pressure of 0.4 to 0.85mpa.
6. The purification process according to claim 2, wherein the operating temperature of the carbon dioxide adsorber (7) and the fluorocarbon adsorber (8) in step C is 20-70 ℃.
7. The purification process according to claim 2, wherein the preparation method of the Ni-Cu-Ce/γ -Al 2O3 catalyst is as follows:
1) Adding Ni (NO 3)2、Cu(NO3)2、Ce(NO3)3 and stirring to obtain Ni-Cu-Ce solution;
2) Adding pure water and gamma-Al 2O3 into the Ni-Cu-Ce solution to carry out loading, and then drying;
3) Roasting in a muffle furnace at 300-400 ℃ for 4-8 hours after drying; and cooling to obtain the Ni-Cu-Ce/gamma-Al 2O3 catalyst.
8. The purification process according to claim 7, wherein the molar ratio of Ni (NO 3)2、Cu(NO3)2、Ce(NO3)3) is (1-10): 1-10.
9. The purification process of claim 2, wherein the modified 4A molecular sieve of step C is prepared by:
a) Adding polyethylenimine and ammonia water into water, and stirring uniformly to obtain a solution;
b) Soaking the 4A molecular sieve into the solution, stirring, and washing the molecular sieve;
c) Then soaking the molecular sieve in a mixed solution containing CaCl 2、Ce(NO3)3;
d) Pretreating the soaked 4A molecular sieve for 1-3 hours at 60-80 ℃, then treating for 8-12 hours at 150-180 ℃, and cooling to obtain the modified 4A molecular sieve.
10. The purification process according to claim 9, wherein the molar ratio of CaCl 2、Ce(NO3)3 is (0.2-5): 1.
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| JP2007055934A (en) * | 2005-08-24 | 2007-03-08 | Showa Denko Kk | Method for production of pentafluoroethane |
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