CN1057750C - 二氟甲烷的生产 - Google Patents
二氟甲烷的生产 Download PDFInfo
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- CN1057750C CN1057750C CN94191525A CN94191525A CN1057750C CN 1057750 C CN1057750 C CN 1057750C CN 94191525 A CN94191525 A CN 94191525A CN 94191525 A CN94191525 A CN 94191525A CN 1057750 C CN1057750 C CN 1057750C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
生产二氟甲烷的方法，包括在氟化催化剂存在下，使二氯甲烷与氟化氢接触，所用的催化剂包括含锌或锌的化合物和一种金属氧化物，氟化物或氟氧化物。
Description
本发明涉及生产二氟甲烷的方法。
近年来国际上日益关注氟氯化碳在世界范围的大规模使用会破坏地球的保护性臭氧层，因此国际立法已提到应有位置，以保证它们的制造和使用要逐步地完全终止。氟氯化碳例如可用作冷冻剂、泡沫材料发泡剂、清洗溶剂和气溶胶喷雾的推进剂，对于它们的多种应用实质上是不应受限制的。因此，正在作出很多努力以寻找氟氯化碳的适宜替代物。这些替代物在很多使用氟氯化碳的应用中应表现出令人满意的性能，而且对臭氧层不能产生上述有害的影响。发现这种适宜替代物的一种途径是集中在对氟碳化物的研究上，它不含氯而含氢。这种氢氟碳化物(hydrofluorocarbon)，二氟甲烷，也称之为HFA32，作为一种替代物是有意义的。特别是，它与其它氢氟碳化物的混合物，例如HFA134a和HFA125，可作为冷冻、空调和其它应用中R-22和R-502的替代物。
已提出了一些生产二氟甲烷的方法。例如美国专利2,744,148描述了生产二氟甲烷的方法，包括在氟化催化剂存在下使二氯甲烷与氟化氢接触，此催化剂包括载于氟化铝上的镍、铬、钴、铜或钯。用于二氯甲烷的氢氟化己提出许多别的催化剂，例如，U.S.4,147,733中的载于氧化铝上的氟化铬；EP128510中的氟化铝、氟化铝及其混合物，载于活性碳上的氟化铝或载于活性碳上的氯化铁；US 2,745,886中的氟氧化铬(Chromium oxyfluoride)和GB1,307,224中的氧化铬。
但是，通过二氯甲烷的氢氟化生产二氟甲烷的严重问题是产生作为中间体的相当大量的高毒性副产物一氯一氟甲烷，HCFC31。HCFC31的职业暴露极限为10PPb和在二氯甲烷的氢氟化的产品中可能产生相当大量的HCFC31，它会占20％或更多。
我们现已发现一些氟化催化剂对二氟甲烷的选择性可以大大提高，因而使HCFC31的产生大大减少。
按照本发明提供一种生产二氟甲烷的方法，包括在氟化催化剂存在下使二氯甲烷与氟化氢接触，所用催化剂包括锌或锌的化合物和一种金属氧化物、氟化物或氟氧化物。
我们乐意选择使用EP0502605或PCT/GB93/00244所述的催化剂，此文献的公开并入本发明作为参考。
因而，此金属或金属氧化物、氟化物或氟氧化物，锌的量，催化剂的制法，催化剂的预氟化处理，催化剂的形式，催化剂的再生处理和催化剂中其它金属或其化合物的存在都在EP0502605或/PCT/GB93/00244，特别是在EP0502605中描述了。这些优选的催化剂制备、形式及组合物也在EP0502605和/PCT/GB93/00244中公开和描述了。
方法进行的条件：温度、压力和原料的量可以是对于二氯甲烷氢氟化所预先提出。这温度可以在约100℃-约500℃的范围内，优选为200℃-400℃。虽然本发明使用催化剂可允许比现有技术中使用的催化剂的温度较低些，而与在较高温度使用如前所述的催化剂产生的HCFC31的水平相比较，产生HCFC31的水平并不增加。使用较低的温度会导致催化剂寿命的大大延长，因而催化剂需要再生的次数也就相应减少。这温度范围更优选为170℃-340℃和特别优选为240℃-320℃。
如需要，虽然可使用高于大气压或低于大气压的压力，但本发明方法一般在大气压下操作。高于大气压如直到30巴的压力也可方便地使用。
通常，使用氟化氢对二氯甲烷的化学计量过量，和氟化氢对二氯甲烷的摩尔比一般至少为3∶1，优选至少为5∶1，和低于100∶1，优选低于50∶1。氟化氢对二氯甲烷的摩尔比最优选范围之5∶1-25∶1。
二氟甲烷可方便地用常规技术如蒸馏从未反应的原料和中间体HCFC31中分离出来。此方法最好连续操作，其中未反应原料和HCFC31再循环。
下面通过实施例具体说明本发明但不限制本发明。
实例1
由共沉淀制备的含有8％(重量)的锌的10克锌/铬混合氧化物催化剂放入1/2”直径的因康镍合金的管式反应器中，在氮气氛中加热至300℃，然后氟化氢在300℃通过催化剂24小时和反应器冷却至250℃。
反应器用氮气加压至10巴，和按表1所示的摩尔比使二氯甲烷和氟化氢通过催化剂。从反应器中排出气体经水洗涤以除去氟化氢和氯化氢，取样和用气相色谱分析。结果示于表1。
表1
HF∶CH2Cl2 排出气体组成(摩尔比) (％体/体)
CH2Cl2 CH2ClF CH2F2
27.1 1.0 7.1 92.0
21.3 2.3 10.1 87.7
19.6 2.8 11.1 86.1
12.5 7.4 9.4 83.1
11.2 6.4 8.9 84.7
11.5 5.4 8.2 86.4
12.2 5.8 8.4 85.7
实例2
重复实例1的程序只是使用大气压力和温度如表2所示。结果见表2。
表2
HF∶CH2Cl2 温度 排出气体组成
(摩尔比) ℃ (％体/体)
CH2Cl2 CH2ClF CH2F2
7.0 210 35.0 12.1 52.9
7.1 230 20.8 10.9 68.3
6.3 250 17.1 11.1 71.9
15.9 250 3.5 5.2 91.3
16.1 200 34.7 11.3 54.0
实例3
重复实例2的程序，只是此催化剂含有2％(重/重)的锌，制备方法是用氯化锌水溶液浸渍具有初始表面积为180米2克的γ-氧化铝。条件和结果见表3。
表3
HF∶CH2Cl2 温度 排出气体组成
(摩尔比) ℃ (％体/体)
CH2Cl2 CH2ClF CH2F2
16.0 200 61.4 15.4 23.2
16.9 200 64.1 15.6 20.3
Claims (5)
1.生产二氟甲烷的方法，包括在氟化催化剂存在下使二氯甲烷与氟化氢接触，所用催化剂包含锌或锌的化合物和一种金属氧化物，氟化物或氟氧化物。
2.如权利要求1的方法，其中该催化剂包含锌或锌的化合物和氧化铬，氟化铬或氟氧化铬。
3.如权利要求1或2的方法，其中温度范围是约240-320℃。
4.如权利要求1或2的方法，其中氟化氢对二氯甲烷的摩尔比范围是约5∶1-25∶1。
5.如权利要求1的方法，其中以催化剂重量为基锌的百分含量为约0.5％-30％。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB939306072A GB9306072D0 (en) | 1993-03-24 | 1993-03-24 | Production of difluoromethane |
| GB9306072.1 | 1993-03-24 | ||
| GB939306089A GB9306089D0 (en) | 1993-03-24 | 1993-03-24 | Production of difluoromethane |
| GB9306089.5 | 1993-03-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1119431A CN1119431A (zh) | 1996-03-27 |
| CN1057750C true CN1057750C (zh) | 2000-10-25 |
Family
ID=26302637
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94191525A Expired - Fee Related CN1057750C (zh) | 1993-03-24 | 1994-03-14 | 二氟甲烷的生产 |
| CN94191526A Expired - Fee Related CN1044227C (zh) | 1993-03-24 | 1994-03-14 | 二氟甲烷的生产 |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94191526A Expired - Fee Related CN1044227C (zh) | 1993-03-24 | 1994-03-14 | 二氟甲烷的生产 |
Country Status (15)
| Country | Link |
|---|---|
| US (2) | US5763704A (zh) |
| EP (2) | EP0690833B1 (zh) |
| JP (2) | JP3631753B2 (zh) |
| KR (2) | KR100323102B1 (zh) |
| CN (2) | CN1057750C (zh) |
| AU (2) | AU691487B2 (zh) |
| BR (2) | BR9406201A (zh) |
| CA (2) | CA2157528C (zh) |
| DE (2) | DE69410455T2 (zh) |
| ES (2) | ES2115940T3 (zh) |
| GB (2) | GB9404715D0 (zh) |
| RU (2) | RU2127246C1 (zh) |
| TW (1) | TW290531B (zh) |
| UA (2) | UA35612C2 (zh) |
| WO (2) | WO1994021580A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372821C (zh) * | 2002-07-10 | 2008-03-05 | Srf有限公司 | 二氟甲烷的制备方法 |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2736050B1 (fr) * | 1995-06-29 | 1997-08-01 | Atochem Elf Sa | Procede de fabrication du difluoromethane |
| US5763708A (en) * | 1995-09-20 | 1998-06-09 | Allied Signal Inc. | Process for the production of difluoromethane |
| FR2748022B1 (fr) * | 1996-04-29 | 1998-07-24 | Atochem Elf Sa | Procede de fabrication du difluoromethane |
| BE1010626A3 (fr) * | 1996-09-16 | 1998-11-03 | Solvay | Procede pour la preparation de difluoromethane. |
| US5800682A (en) * | 1996-10-08 | 1998-09-01 | Alliedsignal Inc. | Process for the production of difluoromethane |
| BE1012227A3 (fr) * | 1998-10-12 | 2000-07-04 | Solvay | Catalyseur et procede d'hydrofluoration. |
| WO2004007410A1 (en) * | 2002-07-10 | 2004-01-22 | Srf Limited | A process for the production of difluoromethane |
| KR100512845B1 (ko) * | 2002-11-21 | 2005-09-07 | 울산화학주식회사 | 디플르오로메탄의 제조 방법 |
| TW200516068A (en) * | 2003-09-10 | 2005-05-16 | Showa Denko Kk | Process for production of hydrofluorocarbons, products thereof and use of the products |
| US7371905B2 (en) * | 2003-10-17 | 2008-05-13 | Honeywell International Inc. | Method of producing hydrofluorocarbons |
| US7112708B2 (en) | 2004-04-01 | 2006-09-26 | Honeywell International Inc. | Method of making difluoromethane, 1,1,1-trifluoroethane and 1,1-difluoroethane |
| MX2011002366A (es) * | 2008-09-05 | 2011-06-27 | Mexichen Amanco Holding Sa De Capital Variable | Catalizador de fluoracion y proceso para producir hidrocarburos fluorados. |
| KR101999136B1 (ko) * | 2011-10-12 | 2019-07-11 | 바이엘 인텔렉쳐 프로퍼티 게엠베하 | 1-클로로-2,2-디플루오로에탄의 제조를 위한 1,1,2-트리클로로에탄 및/또는 1,2-디클로로에텐의 촉매적 기상 불소화 |
| JP2014221727A (ja) * | 2013-05-13 | 2014-11-27 | 昭和電工株式会社 | ジクロロメタンの精製方法およびそれを用いるジフルオロメタンの製造方法 |
| CN114425275B (zh) * | 2020-09-18 | 2023-08-15 | 中国石油化工股份有限公司 | 甲烷氧化偶联反应器及其应用 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0128510A2 (en) * | 1983-06-07 | 1984-12-19 | Showa Denko Kabushiki Kaisha | Process for producing difluoromethane |
| EP0502605A1 (en) * | 1991-03-07 | 1992-09-09 | Imperial Chemical Industries Plc | Fluorination catalyst and process |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2744148A (en) * | 1952-02-04 | 1956-05-01 | Dow Chemical Co | Process for fluorination of haloalkanes using a hydrogen fluoride activated catalyst containing alumina, a metal fluoride and basic aluminum fluoride |
| US2745886A (en) * | 1955-01-31 | 1956-05-15 | Dow Chemical Co | Process for fluorinating aliphatic halohydrocarbons with a chromium fluoride catalyst and process for preparing the catalyst |
| US5300710A (en) * | 1991-03-20 | 1994-04-05 | E. I. Du Pont De Nemours And Company | Process for the manufacture of 2-chloro-1,1,1,2-tetrafluoroethane and pentafluoroethane |
| US5208395A (en) * | 1992-04-06 | 1993-05-04 | Elf Atochem North America, Inc. | Manufacture of hydrofluorocarbons |
| EP0629440B1 (en) * | 1993-06-18 | 1998-01-14 | Showa Denko Kabushiki Kaisha | Fluorination catalyst and fluorination process |
| KR960022411A (ko) * | 1994-12-28 | 1996-07-18 | 남경희 | 디플루오로메탄의 제조방법 |
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1994
- 1994-03-10 GB GB9404715A patent/GB9404715D0/en active Pending
- 1994-03-10 GB GB9404703A patent/GB9404703D0/en active Pending
- 1994-03-14 US US08/522,241 patent/US5763704A/en not_active Expired - Fee Related
- 1994-03-14 WO PCT/GB1994/000498 patent/WO1994021580A1/en active IP Right Grant
- 1994-03-14 ES ES94909203T patent/ES2115940T3/es not_active Expired - Lifetime
- 1994-03-14 BR BR9406201A patent/BR9406201A/pt not_active IP Right Cessation
- 1994-03-14 JP JP52076394A patent/JP3631753B2/ja not_active Expired - Fee Related
- 1994-03-14 UA UA95094274A patent/UA35612C2/uk unknown
- 1994-03-14 EP EP94909204A patent/EP0690833B1/en not_active Expired - Lifetime
- 1994-03-14 EP EP94909203A patent/EP0690832B1/en not_active Expired - Lifetime
- 1994-03-14 CA CA002157528A patent/CA2157528C/en not_active Expired - Fee Related
- 1994-03-14 DE DE69410455T patent/DE69410455T2/de not_active Expired - Fee Related
- 1994-03-14 DE DE69410456T patent/DE69410456T2/de not_active Expired - Fee Related
- 1994-03-14 KR KR1019950704055A patent/KR100323102B1/ko not_active IP Right Cessation
- 1994-03-14 AU AU62134/94A patent/AU691487B2/en not_active Ceased
- 1994-03-14 US US08/507,429 patent/US5672786A/en not_active Expired - Fee Related
- 1994-03-14 CA CA002157878A patent/CA2157878C/en not_active Expired - Fee Related
- 1994-03-14 CN CN94191525A patent/CN1057750C/zh not_active Expired - Fee Related
- 1994-03-14 RU RU95121816A patent/RU2127246C1/ru not_active IP Right Cessation
- 1994-03-14 AU AU62133/94A patent/AU691486B2/en not_active Ceased
- 1994-03-14 KR KR1019950704025A patent/KR100323101B1/ko not_active IP Right Cessation
- 1994-03-14 CN CN94191526A patent/CN1044227C/zh not_active Expired - Fee Related
- 1994-03-14 ES ES94909204T patent/ES2116586T3/es not_active Expired - Lifetime
- 1994-03-14 JP JP6520764A patent/JPH08508029A/ja not_active Ceased
- 1994-03-14 UA UA95094235A patent/UA40612C2/uk unknown
- 1994-03-14 RU RU95118158A patent/RU2116288C1/ru not_active IP Right Cessation
- 1994-03-14 BR BR9406236A patent/BR9406236A/pt not_active IP Right Cessation
- 1994-03-14 WO PCT/GB1994/000497 patent/WO1994021579A1/en active IP Right Grant
- 1994-03-18 TW TW083102380A patent/TW290531B/zh active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0128510A2 (en) * | 1983-06-07 | 1984-12-19 | Showa Denko Kabushiki Kaisha | Process for producing difluoromethane |
| EP0502605A1 (en) * | 1991-03-07 | 1992-09-09 | Imperial Chemical Industries Plc | Fluorination catalyst and process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372821C (zh) * | 2002-07-10 | 2008-03-05 | Srf有限公司 | 二氟甲烷的制备方法 |
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