CN1043342C - 含氟烯烃混合气加氢制造1.1.1.2-四氟乙烷制冷工质的方法 - Google Patents
含氟烯烃混合气加氢制造1.1.1.2-四氟乙烷制冷工质的方法 Download PDFInfo
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- CN1043342C CN1043342C CN 93106145 CN93106145A CN1043342C CN 1043342 C CN1043342 C CN 1043342C CN 93106145 CN93106145 CN 93106145 CN 93106145 A CN93106145 A CN 93106145A CN 1043342 C CN1043342 C CN 1043342C
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- 238000005984 hydrogenation reaction Methods 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 27
- 239000011737 fluorine Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 22
- 238000005057 refrigeration Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000008246 gaseous mixture Substances 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000005336 cracking Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010790 dilution Methods 0.000 abstract description 3
- 239000012895 dilution Substances 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 5
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract 4
- 229930195733 hydrocarbon Natural products 0.000 abstract 2
- 239000012188 paraffin wax Substances 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 230000006378 damage Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 2
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
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Abstract
本发明公开了一种含氟烯烃混合气加氢制造1.1.1.2-四氟乙烷制冷工质的方法,它是用主要含有四氟乙烯混合含氟烯烃经一步法加压催化加氢得到混合含氟烷烃(HFC),然后分离得到1.1.1.2-四氟乙烷制冷工质。所用的催化剂为含Pd及Cr2O3的活性炭或Al2O3,而活性炭催化剂含Pd1~10%(wt),含Cr2O310~30%(wt)且含Pd4~6%最好。混合含氟烯烃和氢的比例为1∶1~1∶10(摩尔比),反应压力为0.1~1MPa,反应温度为450~550℃。本发明简化了工艺,原料价廉,副反应少,并且不须用氮稀释。
Description
本发明涉及制造1.1.1.2-四氟乙烷(HFCl34a)制冷工质的方法,尤其是涉及含氟烯烃混合气加氢制造1.1.1.2-四氟乙烷制冷工质的方法。
CFC12(CCl2F2)或称R12、F12,是广泛使用的制冷工质。由于具有强烈破坏大气臭氧层的作用(耗竭臭氧层潜势“ODP”值等于1.0),严重危害人类和其它生物的生存环境,国际上已协议决定限制其生产和使用。对臭氧层无害(其ODP值等于0)的HFC134a(CH2FCF3)是目前国际上公认的CF12的首选替代品。国内外有关技术均采用取代反应制造HFC134a,仅欧洲专利European Patent 0365296(1990.4.25)提出过用纯C2F4加氢以制造HFC134a的加成反应技术路线。其方法为两步法,即首先将H2与纯C2H4以10∶1的体积比通过含Pd的Al2O3催化剂,冷凝后获得HFC134,然后将HFC134用N2稀释(体积比1∶2),通过Cr2O3催化剂异构化,得到HFC134a。
本发明的目的是提供一种含氟烯烃混合气为原料一步法加氢制造1.1.1.2-四氟乙烷制冷工质的方法。
为了达到上述目的本发明采取下列措施,一种含氟烯烃混合气加氢制造1.1.1.2-四氟乙烷制冷工质的方法,特征是用主要含有四氟乙烯的混合含氟烯烃经一步法加压催化加氢得到混合含氟烷烃(HFC),然后分离得到1.1.1.2-四氟乙烷制冷工质,催化剂为含Pd及Cr2O3的活性炭或Al2O3,活性炭催化剂含Pd1~10%(wt),含Cr2O310~30%(wt),含氟烯烃和氢的比例为1∶1~1∶10(摩尔比),反应压力为0.1~1MPa,反应温度为450~550℃
本发明的优点:
1.本发明采用由裂解二氟一氯甲烷制得的混合的含氟烯烃主要含有四氟乙烯(C2F4)作原料加氢,而不用纯C2F4为原料,其基本工艺方法是用HCF22(CHCIF2)热裂解(空管裂解或过热水蒸汽裂解)。含氟烯烃混合气是该方法的中间产物。该混合气中除C2F4外尚含有C2HF3,C2H2F4。这些含氟烯烃的混合物(已除去HCI和未裂解的HCFC22)难于用一般的蒸馏方法加以分离,须采用萃取精馏等特殊技术,因而纯C2F4比较昂贵。若用发明的方法,原料比较便宜,制得的HFC134a较的竞争力。
2.用混合含氟烯烃加氢,不仅得到主产品HFC134a,而且可以得到HFC143a,HFC152a和HFC125等副产物,均为ODP值等于0对大气臭氧层无害的各种制冷工质,都是极有价值的产品。它们之间沸点差清晰,比混合含氟烯烃容易分离得多,可以用普通精馏方法一一提纯。
3.纯C2F4极易爆聚而发生爆炸,因此用纯C2F4加氢制造HFC134a,只能采用低温常压的条件,效率必然很低。而本发明由于采用混合气体,C2F4纯度低,因此比较安全,可适当加压,以提高加氢效率,对产物的分离也有利。
4.本发明一步生成HFC134a比两步法简化了工艺,并且由于反应过程中存在的异构化反应是在伴有大量氢气的气氛下进行的,因此裂解副反应较少,并且不须用氮稀释。
下面结合实施例作详细说明。
含氟烯烃混合气加氢制造1.1.1.2-四氟乙烷制冷工质的方法,特征是活性炭催化剂含Pd为4~6%(wt)。反应压力为0.4~0.6MPa。
实施例:
氢和含氟烯烃(成分见表1),以10∶1(摩尔比)的比例混和,在0.5MPa的压力下通过一装有含5%(wt)Pd和20%(wt)Cr2O3的活性炭的催化剂的反应管,反应管温度为500℃,催化剂的负荷为0.6ml/ml·min,获得的产物去除氢以后的成分如表2所示。含氟烯烃的总转化率超过95%,HFC134a的选择性为80%左右(C2H2F4)。
表1含氟烯烃混合物的成分(mole%)
表2反应物成分(mole%)
C2F4 | C2HF3 | C2H2F2 | C3F6 |
98.6 | 0.4 | 0.3 | 0.7 |
试验编号 | 1 | 2 | 3 | 4 |
HFC134a | 55.7 | 62.2 | 67.3 | 68.2 |
HFC134 | 13.3 | 14.4 | 14.3 | 11.2 |
HFC143a | 12.7 | 12.6 | 10.7 | 9.5 |
HFC152A | 1.9 | 2.2 | 0.9 | 1.0 |
HFC125 | 12.0 | 7.7 | 6.5 | 9.4 |
C2F4 | 4.1 | 0.7 | - | 0.5 |
HFC236 | 0.1 | 0.1 | 0.1 | 0.1 |
Claims (3)
1.一种含氟烯烃混合气加氢制造1.1.1.2-四氟乙烷制冷工质的方法,其特征在于用主要含有四氟乙烯混合含氟烯烃经一步法加压催化加氢得到混合含氟烷烃(HFC),然后分离得到1.1.1.2-四氟乙烷制冷工质,催化剂为含Pd及Cr2O3的活性炭或Al2O3,活性炭催化剂含Pd1~10%(wt),含Cr2O310~30%(wt),含氟烯烃和氢的比例为1∶1~1∶10(摩尔比),反应压力为0.1~1MPa,反应温度为450~550℃。
2.根据权利要求1所述的一种含氟烯烃混合气加氢制造1.1.1.2-四氟乙烷制冷工质的方法,其特征在于所说的活性炭催化剂含Pd为4~6%(wt)。
3.根据权利要求1或2所述的一种含氟烯烃混合气加氢制造1.1.1.2-四氟乙烷制冷工质的方法,其特征在于反应压力为0.4~0.6MPa。
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CN 93106145 CN1043342C (zh) | 1993-05-21 | 1993-05-21 | 含氟烯烃混合气加氢制造1.1.1.2-四氟乙烷制冷工质的方法 |
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