JP5136111B2 - フルオロオレフィンとフッ化水素の分離方法 - Google Patents
フルオロオレフィンとフッ化水素の分離方法 Download PDFInfo
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- JP5136111B2 JP5136111B2 JP2008037209A JP2008037209A JP5136111B2 JP 5136111 B2 JP5136111 B2 JP 5136111B2 JP 2008037209 A JP2008037209 A JP 2008037209A JP 2008037209 A JP2008037209 A JP 2008037209A JP 5136111 B2 JP5136111 B2 JP 5136111B2
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- hydrogen fluoride
- sulfuric acid
- fluoroolefin
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims description 74
- 229910000040 hydrogen fluoride Inorganic materials 0.000 title claims description 74
- 238000000034 method Methods 0.000 title claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 84
- 239000000203 mixture Substances 0.000 claims description 37
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 claims description 21
- PGJHURKAWUJHLJ-UHFFFAOYSA-N 1,1,2,3-tetrafluoroprop-1-ene Chemical compound FCC(F)=C(F)F PGJHURKAWUJHLJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012071 phase Substances 0.000 description 27
- 238000005406 washing Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001722 carbon compounds Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- FYIRUPZTYPILDH-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoropropane Chemical compound FC(F)C(F)C(F)(F)F FYIRUPZTYPILDH-UHFFFAOYSA-N 0.000 description 1
- NLOLSXYRJFEOTA-UHFFFAOYSA-N 1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)C=CC(F)(F)F NLOLSXYRJFEOTA-UHFFFAOYSA-N 0.000 description 1
- DMUPYMORYHFFCT-UHFFFAOYSA-N 1,2,3,3,3-pentafluoroprop-1-ene Chemical compound FC=C(F)C(F)(F)F DMUPYMORYHFFCT-UHFFFAOYSA-N 0.000 description 1
- WFOIWBGKCSYBJN-UHFFFAOYSA-N 1-fluorobut-1-ene Chemical compound CCC=CF WFOIWBGKCSYBJN-UHFFFAOYSA-N 0.000 description 1
- VJGCZWVJDRIHNC-UHFFFAOYSA-N 1-fluoroprop-1-ene Chemical compound CC=CF VJGCZWVJDRIHNC-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 1
- DKSYJUPLFVFPRY-UHFFFAOYSA-N 2,4,4,4-tetrafluorobut-1-ene Chemical compound FC(=C)CC(F)(F)F DKSYJUPLFVFPRY-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- -1 fluorocarbon Chemical compound 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
[1]1,3,3,3−テトラフルオロプロペンとフッ化水素を含む混合物から1,3,3,3−テトラフルオロプロペン又はフッ化水素を分離する方法であって、1,3,3,3−テトラフルオロプロペンとフッ化水素を含む混合物を硫酸と接触させる工程、1,3,3,3−テトラフルオロプロペンが50質量%を超える第1相とフッ化水素及び硫酸を含んでなる第2相を形成する工程、並びに1,3,3,3−テトラフルオロプロペンが50質量%を超える第1相をフッ化水素及び硫酸を含んでなる第2相から分ける工程を含み、硫酸のフッ化水素に対する質量比が2:1〜20:1である方法。
[2]1,3,3,3−テトラフルオロプロペンとフッ化水素を含む混合物が共沸混合物である上述の方法。
本発明の混合物においては、ハイドロフルオロカーボンの自己分解反応生成物であることが好ましい。自己分解反応としては、熱分解又はアルミナ、ジルコニア、炭素又はそれらにアルミニウム、クロムなどを担持された触媒を使用した接触分解が挙げられるがこれらに限られない。これらの自己分解反応は通常気相で、また、温度を高めた状態、加圧もしくは減圧下で行うことができる。フルオロカーボン、ハイドロフルオロカーボン、ハイドロカーボンなどのふっ化水素に対して不活性な溶媒を用いても行うこともできる。
200mlのSUS304製耐圧容器に114gの1,3,3,3−テトラフルオロプロペンと20gのフッ化水素を溶解して均一な1,3,3,3−テトラフルオロプロペン/フッ化水素混合物を形成させた後、窒素で0.8MPaG(「G」はゲージ圧をいう。以下同じ。)まで加圧した。次いで、別の300mlのSUS304製耐圧容器に100gの工業用硫酸(純度98%以上)を注入した後に−0.1MPaGまで減圧した。この硫酸に前記1,3,3,3−テトラフルオロプロペン/フッ化水素混合物を液状で流量調整弁を通して少量ずつ加えていくと発熱が見られた。全量移液後、形成した2層のうち下層(第2相)を容器下部の弁から分取したところ、119gのフッ化水素/硫酸混合物が得られた。上層(第1相)は、ガス状態で抜き出し洗浄水をくぐらせた後、−78℃のドライアイストラップで液化回収した。回収量は111gであり、1,3,3,3−テトラフルオロプロペンの回収率は97質量%であった。洗浄水を分析したところ、微量の酸が検出され、0.1N水酸化ナトリウム溶液で滴定を行ったところフッ化水素換算で約1g検出された。検出されたフッ化水素の値から抽出効率を計算すると95質量%であった。
容量4リットルのSUS304製容器の上部に、SUS304製6mmφラシヒリングを充填した内径32mm、高さ800mmのSUS304製吸収塔を備えた洗浄塔の底部に、3000gの工業用硫酸を仕込み、硫酸をポンプで塔頂部に送液しながら循環させた。一方、容量5リットルのSUS304製耐圧容器に3420gの1,3,3,3−テトラフルオロプロペンと600gのフッ化水素を溶かして均一な混合物を形成させた後、窒素で0.8MPaGまで加圧した。この混合物の全量を液状で一定量ずつ抜き出してガス状にしながら洗浄塔底部に導入し、硫酸と向流で接触させた。塔頂部から出てきた1,3,3,3−テトラフルオロプロペンは洗浄水をくぐらせた後、−78℃のドライアイストラップで液化回収した。回収量は3249gであり、1,3,3,3−テトラフルオロプロペンの回収率は95質量%であった。洗浄水を分析したところ、酸が検出された。0.5N水酸化ナトリウム溶液で滴定を行ったところ、フッ化水素換算24gの酸であった。検出されたフッ化水素の値から抽出効率を計算すると96質量%であった。洗浄塔内に残ったフッ化水素と硫酸の混合物を5リットルのSUS304製蒸留装置に移し、塔底の温度を徐々に上げながら蒸留したところ100℃で終了するまでに180gのフッ化水素が回収された。これをイオンクロマトグラフィで分析したところ硫酸イオンは検出されなかった。
Claims (2)
- 1,3,3,3−テトラフルオロプロペンとフッ化水素を含む混合物から1,3,3,3−テトラフルオロプロペン又はフッ化水素を分離する方法であって、1,3,3,3−テトラフルオロプロペンとフッ化水素を含む混合物を硫酸と接触させる工程、1,3,3,3−テトラフルオロプロペンが50質量%を超える第1相とフッ化水素及び硫酸を含んでなる第2相を形成する工程、並びに1,3,3,3−テトラフルオロプロペンが50質量%を超える第1相をフッ化水素及び硫酸を含んでなる第2相から分ける工程を含み、硫酸のフッ化水素に対する質量比が2:1〜20:1である方法。
- 1,3,3,3−テトラフルオロプロペンとフッ化水素を含む混合物が共沸混合物である請求項1に記載の方法。
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US8058486B2 (en) * | 2004-04-29 | 2011-11-15 | Honeywell International Inc. | Integrated process to produce 2,3,3,3-tetrafluoropropene |
US8747691B2 (en) | 2010-05-06 | 2014-06-10 | Honeywell International Inc. | Azeotrope-like compositions of tetrafluoropropene and water |
JP5817373B2 (ja) * | 2010-11-10 | 2015-11-18 | セントラル硝子株式会社 | トランス−1,3,3,3−テトラフルオロプロペンの製造方法 |
US9272968B2 (en) | 2013-03-14 | 2016-03-01 | Honeywell International Inc. | Process to suppress the formation of 3,3,3-trifluoropropyne in fluorocarbon manufacture |
CN107522592B (zh) * | 2017-09-07 | 2020-06-02 | 浙江衢化氟化学有限公司 | 一种联产多种卤代烯烃和氟代烷烃的方法 |
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US3873629A (en) * | 1974-01-23 | 1975-03-25 | Du Pont | Separation of chlorodifluoromethane and hydrogen |
US5895639A (en) * | 1996-07-03 | 1999-04-20 | Alliedsignal Inc. | Separation of hydrogen fluoride from a fluorocarbon/hydrogen fluoride azeotropic mixture by sulfuric acid |
US7423188B2 (en) * | 2005-11-01 | 2008-09-09 | E. I. Du Pont De Nemours And Company | Azeotrope compositions comprising E-1,3,3,3-tetrafluoropropene and hydrogen fluoride and uses thereof |
US7560602B2 (en) * | 2005-11-03 | 2009-07-14 | Honeywell International Inc. | Process for manufacture of fluorinated olefins |
US7722781B2 (en) * | 2006-06-27 | 2010-05-25 | E.I. Du Pont De Nemours And Company | Tetrafluoropropene production processes |
EP2054361B1 (en) * | 2006-08-24 | 2016-02-17 | E. I. du Pont de Nemours and Company | Processes for separation of fluoroolefins from hydrogen fluoride by azeotropic distillation |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |