GB2101596A - Oxychlorination of alkanes to monochlorinated olefins - Google Patents
Oxychlorination of alkanes to monochlorinated olefins Download PDFInfo
- Publication number
- GB2101596A GB2101596A GB08217898A GB8217898A GB2101596A GB 2101596 A GB2101596 A GB 2101596A GB 08217898 A GB08217898 A GB 08217898A GB 8217898 A GB8217898 A GB 8217898A GB 2101596 A GB2101596 A GB 2101596A
- Authority
- GB
- United Kingdom
- Prior art keywords
- alkane
- process according
- catalyst
- mixture
- ethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
- C07C17/154—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of saturated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for the production of a monochlorinated olefin comprises bringing into reaction at an elevated temperature a gaseous mixture comprising an alkane, a source of chlorine and molecular oxygen in the presence of a solid particulate catalyst composition comprising compounds of copper, manganese and titanium, and is useful for the production of vinyl chloride from ethane.
Description
SPECIFICATION
Production of monochlorinated compounds
The present process relates to the production of monochlorinated compounds by the oxychlorination of alkanes.
Vinyl chloride is at present manufactured in an essentially two stage process by the oxychlorination of ethylene. Since ethane is potentially a much cheaper feedstock there is considerable incentive to devise a suitable alternative process, particularly if a single stage process can be developed.
Several possible processes have been disclosed (e.g. US 3,937,744; Ger Off 2,540,067; US 3,629,351 and GB2009164). In general these employ similar catalysts to those employed for ethylene oxychlorination, but it is generally found that much higher reaction temperatures are required (450-7000C as compared with about 3500--5000C). This is a serious disadvantage since the catalyst can be molten or partially volatile (necessitating a complex reactor design) and the highly corrosive reaction conditions require the use of expensive construction materials.
We have now discovered certain catalysts which can operate in a temperature region substantially below that hitherto possible and thus reduce corrosion/erosion problems. The catalysts may be used in the solid particulate state, thus avoiding reactor problems associated with molten salts and permitting the use of both fixed and fluid bed reactors. These catalysts thus afford the advantage of a selective single stage process based on ethane feedstock.
According to the present invention, we provide a process for the production of a monochlorinated olefin which comprises bringing into reaction at an elevated temperature a gaseous mixture comprising an alkane, a source of chlorine and molecular oxygen in the presence of a solid particulate catalyst composition comprising compounds of copper, manganese and titanium.
The catalyst composition may include one or more additional components, for example, cerium, thorium, iron or zinc compounds.
The process of the invention is applicable to a range of alkane starting materials, especially alkanes having 2 to 4 carbon atoms, for example ethane. The starting material may comprise an alkane/alkene mixture. The alkene may be, for example, ethylene, propylene and various butenes.
The process of the invention is especially applicable to the production of vinyl chloride from ethane orethane/ethylene mixture.
Suitable catalyst compositions include those in which the atomic ratio of copper: manganese :titanium is in the range 1:0.1:1 to 1 :10:25. Particularly valuable results are obtained when this ratio is substantially 1:1:10.
When additional components are present, the atomic ratio of each additional metal relative to the copper present is suitably within the range 0.1 to 5. Particularly valuable results have been obtained when the atomic ratio Cu: Mn :X : Ti is substantially 1:1:0.5:0.5:10, the metals X and Y being selected from Ce, Th, Fe and Zn.
The catalyst may conveniently be prepared by coprecipitation of the appropriate oxides, which coprecipitation may be effected chemically, thermally or electrically, or by a combination of these methods. Suitably, the coprecipitation comprises preparing a solution containing the materials from which the desired components can be precipitated. Alternatively, the catalysts may be prepared by sintering the components or by combining the molten components. Under reaction conditions, the oxides may be converted partly or wholly to the corresponding chlorides and/or oxychlorides.
The catalyst may be supported if desired on known carriers such as, for example, silica, alumina, titania or silicon carbide. The surface area of the support can be varied widely but is usually in the range 0.1 to 50 m2/g.
The supported catalyst may be employed in fixed, moving or fluidised beds of the appropriate size.
The reaction temperature may vary according to the reactant employed. Suitably, for example for the oxychlorination of ethane or ethane/ethylene, the reaction temperatures are in the range 2500C-5000C, for example 3000C-4750C. The reaction is normally carried out under atmospheric or superatmospheric pressure, e.g. at a pressure in the range 1 to 100 bars.
The source of oxygen may be oxygen itself or oxygen enriched air. The molar ratios of alkane or alkane/alkene mixture and oxygen are preferably in the range 0.1 to 10 moles of oxygen for each mole of alkane or alkane-alkene mixture, for example 0.5 to 2 moles of oxygen for each mole of alkane or alkane/alkene mixture.
The source of chlorine is suitably hydrogen chloride or a mixture of chlorine itself and hydrogen chloride, or a mixture of hydrogen chloride and/or chlorine and chlorinated hydrocarbons (e.g.
chlorohydrocarbons such as ethyl chloride, ethylene dichloride). It is preferred to use hydrogen chloride or a mixture of chlorine and hydrogen chloride (including ammonium chloride which on heating decomposes to give hydrogen chloride). Typically, the reaction mixture contains 0.1 to 10 moles of hydrogen chloride, for example 1 to 3 moles of hydrogen chloride for each mole of alkane or alkane/alkene mixture.
The products of the reaction may be isolated and used as such or, if desired, may be recycled wholly or partially to the reactor in order to increase the yield of monochlorinated olefin, e.g. vinyl chloride.
The invention is illustrated by the following Examples.
EXAMPLE 1
A Cu/Mn/Ti catalyst was prepared as follows: to 170 ml of a 1 5% solution of titanium tetrachloride was added an equal volume of water, followed by ammonium hydroxide until the pH of the solution was greater than 7.0. The resulting precipitate was filtered and washed until free from chloride.
To this precipitate was added a mixture of 6.5 ml of a 50% solution of Mn(NO3)2.6 H2O and 3.62 g of Cu(NO3)2.3 H2O dissolved in 40 ml of water. The resulting mixture was evaporated to dryness, heated at 1200C for 16 hours and finally calcined at 5000C for 16 hours.
After grinding to250-500 m mesh size, the catalyst was loaded into a ;" O.D. tubular micro reactor (equipped with an on-line G.L.C. system) to give a bed length of 5 cm or 10 cm. The catalyst was pretreated in a current of HCI for 1 hour at 4000C followed by N2 for 1 5 minutes at250 C.
Catalytic performance was then evaluated under a range of gas feed conditions and over a range of temperatures. The products were analysed using on-line G.L.C. The results obtained are shown in Table 1.
The catalyst used in this Example had a Cu : Mn Ti atomic ratio of 1:1:10.
EXAMPLE 2
A Cu/Mn/Ti catalyst was prepared and tested as in Example 1 but with an atomic ratio of 1 :1 :15.
The results given in Table2 were obtained with a feed rate of25 ml mien~1 air, 5 ml min-1 ethane and 5 ml min-1 HCl.
EXAMPLE 3
A Cu/Mn/Ti catalyst having an atomic ratio of 1:4:4 was prepared and tested as in Example 1.
Results are summarised in Table 3.
TABLE 1
Selectivity % ml min-1 Cis & BR< temp. Conversion Trans Air Ethane HCl C. % CO2 C2H4 VC EC D.C.E. E.D.C.
25 5 5 400 49.64 14.26 14.53 28.60 0.48 13.56 25.98 25 5 5 425 56.46 9.97 23.58 37.79 0.24 9.34 16.25 25 5 5 450 64.20 6.59 35.55 40.02 0.28 6.36 8.34 25 5 5 475 65.57 7.21 52.94 30.88 0.43 2.80 2.58 25 5 5 500 62.57 9.41 72.05 13.13 0.47 0.68 0.76 REPEAT PREPARATION OF EXAMPLE 1
25 5 5 350 48.15 11.74 4.94 9.52 2.96 22.62 43.15 25 5 5 400 56.81 6.94 13.65 34.68 0.40 18.03 23.48 25 5 5 425 59.73 6.49 23.35 42.27 0.50 11.98 12.94 25 5 5 450 63.50 6.06 37.54 40.82 0.72 6.87 5.72 25 5 5 475 65.41 6.65 54.36 30.74 0.87 2.95 1.91 25 5 5 500 64.26 8.08 74.17 13.94 0.82 0 0 TABLE 2
Selectivity % Temp. Conversion Cis Trans C % CO2 C2H4 VC EC D.C.E. D.C.E. E.D.C. ss Tri 400 50.2 6.0 1.4 0.5 20.9 2.9 1.7 63.1 450 77.4 6.0 13.5 19.4 0.1 11.1 6.6 40.8 2.3 475 83.3 5.6 28.0 29.9 2.5 8.1 4.7 19.3 500 86.5 6.6 49.5 29.5 0.2 4.6 2.8 4.8 TABLE 3
Selectivity % Temp. Conversion Cis Trans C % CO2 C2H4 VC EC D.C.E. D.C.E. E.D.C. ss Tri 400 44 16 3.3 1.7 7.2 9.4 6.1 48.8 2.3 425 81.8 12.0 8.5 8.8 0.5 15.5 9.4 36.3 1.1 450 60.2 17.3 18.8 25.4 - 14.4 8.5 18.0 500 74.1 9.1 44.1 27.2 - 7.6 4.7 4.0 EXAMPLE 4
A Cu/Ce/Th/Mn/Ti catalyst was prepared in the following manner: to 85 ml of a 15% solution of
TiCI4 was added2.038 g of (NH4)2Ce(NO3)6 dissolved in 30 ml water and a solution of 2.234, g of
Th(NO3)4.6 H20 in 55 ml water.To the resulting mixture 50 ml of 25% NH40H was added to give a pale yellow precipitate which was filtered and washed with water until the washings were no longer alkaline.
A mixture of 1.819 g Cu(N03)23 H2O in 40 ml of water and 3.2 ml of a 50% solution of,Mn(NO3)2.6 H2O was added to the yellow precipitate and allowed to stand for 1 6 hours. The mixture was then evaporated to dryness and heated overnight at 1200C. The temperature of the furnace was gradually increased to 5O00C, after which the catalyst was calcined for 16 hours at 5000 C. The catalytic performance was then evaluated in a microreactor as in Example 1 and the results obtained are shown in Table 4.
The catalyst used in this Example had a Cu:Ce;Th:Mn:Ti atomic ratio of 1:0.5 :0.5:1:10
EXAMPLE 5
A Cu/Me/Fe/Ti catalyst was made in the following manner: a solution of 85 ml of 1 5% TiCl4 was mixed with 3.03 g of Fe(NO3)3.9 H2O dissolved in 10 ml water and the resulting mixture diluted with an equal volume of water. A25% solution of NH40H was added (60 mi) to give a yellow-brown precipitate which was then allowed to stand overnight. The precipitate was filtered and washed alkaline-free. To this precipitate was added a mixture of 1.609 g Cu(NO3)2.3 H2O in 40 ml water and 3.2 mol of a 50% solution of Mn(NO3)2.6 H2O. When the addition was complete, the resulting slurry was thoroughly stirred and allowed to stand for 16 hours.The mixture was then evaporated to dryness, dried overnight at 1200C and finally calcined at 5000C for 1 6 hours. The catalyst was packed into a microreactor and tested as in Example 1. The results obtained are shown in Table 5.
TABLE 4
Selectivity % ml min-1 Temp. Conversion Cis Trans Air Ethane HCl C % CO2 C2H4 VC EC D.C.E. D.C.E. E.D.C.
25 5 5 350 26.45 6.35 1.07 0.28 15.31 2.36 1.28 72.44 25 5 5 400 56.62 14.14 17.76 23.97 0 10.59 5.11 26.45 25 5 5 425 71.17 12.73 24.72 33.08 0 10.19 5.02 12.54 25 5 5 400 82.79 7.95 35.31 31.99 0 13.73 4.68 4.77 12.5 2.5 2.5 400 48.16 19.05 12.34 27.17 0 10.88 5.62 22.92 12.5 2.5 2.5 425 58.40 15.11 18.56 36.99 0 10.21 5.23 12.34 12.5 2.5 2.5 425 62.61 12.65 13.92 37.43 0 13.65 7.01 13.61 12.5 2.5 5.0 425 67.76 3.61 8.33 34.58 0 20.98 11.20 19.19 12.5 2.5 6.0 425 36.67 1.82 36.71 32.42 0.21 6.87 3.11 18.39 TABLE 5
Selectivity % ml min-1 Temp. Conversion Cis Trans Air Ethane HCl C % CO2 C2H4 VC EC D.C.E. D.C.E. E.D.C.
25 5 5 350 27.50 10.15 0.97 0.25 17.64 1.66 0.88 64.91 25 5 5 400 53.17 24.22 18.77 16.22 0.08 9.95 5.97 21.52 25 5 5 450 58.33 17.56 28.62 31.44 0.08 8.45 5.23 6.08 25 5 5 500 79.35 8.53 52.63 29.12 0.26 4.93 2.90 0.15 The catalyst used in this Example had a Cu :Mn :Fe :Ti aromic ratio of 1:1:1:10.
EXAMPLE 6
A Cu/Mn/Zn/Ti catalyst was prepared as follows: a solution of 3.718 g of Zn(NO)3)2.6 H2O in 100 ml of water was mixed with 11 3 ml of a 50% solution of TiCI4. The solution was made ammoniacal by the addition of NH4OH and the resulting precipitate filtered and washed until alkali-free. To the washed precipitate was added a mixture of 3.02 g Cu(NO3)2.3H2O in 35 ml water and 5.3 ml of 50%
Mn(NO3)2.6H2O. The mixture was a evaporated to dryness, dried for 16 hours at 120 C and finally calcined at 500 C for 16 hours. The catalyst was packed into a microreactor and its catalytic performance evaluated as in Example 1 and the results obtained are shown in Table 6.
The catalyst used in this Example had a Cu : Mn Zn Ti atomic ratio of 1 :1 :1 :8.
Notes on Tables 1-7 VC = vinyl chloride
EC = ethyl chloride
Cis D.C.E. = cis dichloroethylene
Trans D.C.E. = trans dichloroethylene
EDC = ethylene dichloride ss Tri = ss-trichloroethane TABLE 6
Selectivity % ml min-1 Temp. Conversion Cis trans Air Ethane HCl C % CO2 C2H4 VC EC D.C.E. D.C.E. E.D.C.
25 5 5 400 43.02 16.22 3.78 15.62 0.22 23.66 15.05 19.95 25 5 5 425 53.32 17.78 9.95 34.22 0 15.99 9.31 8.00 25 5 5 450 57.29 16.13 19.48 38.35 0.15 13.50 7.88 1.36 25 5 5 475 63.70 12.37 33.29 34.04 0.13 10.29 6.07 0.17 25 5 5 500 73.95 8.85 49.36 27.07 0.03 7.24 4.30 0 EXAMPLE 7
A range of compositions of Cu/Mn/Zn/Ti catalysts were prepared and evaluated as in Example 6.
The results of reaction at 4500C are summarised in Table 7. TABLE 7
Catalyst Comp. Selectivity % (atomic) Temp. Conv. Cis Trans Cu Mn Zn Ti % % CO2 C2H4 VC EC D.C.E. D.C.E. E.D.C. ss Tri 1 1 1 1 450 57.6 13.4 1.4 5.5 2.4 15.1 7.4 32.0 7.5 1 1 1 2 450 60.1 12.9 14.6 31.9 - 14.3 7.0 15.1 1 1 1 6 450 53.6 18.4 36.5 36.5 - 14.4 8.1 1.2 1 1 1 9 450 62.4 13.5 19.9 40.0 0.1 12.5 7.0 4.0 1 1 2 25 450 49.0 14.9 6.4 15.9 0.1 26.4 16.0 4.4 1 1 2 10 450 82.7 25.4 5.4 16.6 - 22.2 14.1 1.3 5.4 1 2 1 8 450 67.2 21.1 6.7 27.1 - 14.8 10.6 12.2
Claims (8)
1. A process for the production of a monochlorinated olefin which comprises bringing into reaction at an elevated temperature a gaseous mixture comprising an alkane, a source of chlorine and molecular oxygen in the presence of a solid particulate catalyst composition comprising compounds of copper, manganese and titanium.
2. A process according to claim 1 wherein the catalyst composition also includes one or more compounds of cerium, thorium, iron or zinc.
3. A process according to claim 1 or claim2 wherein the alkane is ethane.
4. A process according to any one of the preceding claims wherein the catalyst composition is such that the atomic ratio of copper: manganese :titanium is in the range 1:0.1:1 to 1:10:25.
5. A process according to claim 4 wherein the atomic ratio of copper:manganese :titanium is substantially 1:1:10.
6. A process according to any one of the preceding claims wherein the gaseous mixture contains from 0.1 to 10 moles of oxygen for each mole of alkane.
7. A process according to claim 6 wherein the gaseous mixture contains from 0.5 to 2 moles of oxygen for each mole of alkane.
8. A process according to claim 1 substantially as hereinbefore described with reference to any one of the foregoing Examples.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08217898A GB2101596B (en) | 1981-07-14 | 1982-06-21 | Oxychlorination of alkanes to monochlorinated olefins |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8121710 | 1981-07-14 | ||
| GB08217898A GB2101596B (en) | 1981-07-14 | 1982-06-21 | Oxychlorination of alkanes to monochlorinated olefins |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2101596A true GB2101596A (en) | 1983-01-19 |
| GB2101596B GB2101596B (en) | 1985-11-06 |
Family
ID=26280124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08217898A Expired GB2101596B (en) | 1981-07-14 | 1982-06-21 | Oxychlorination of alkanes to monochlorinated olefins |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2101596B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995007251A1 (en) * | 1993-09-07 | 1995-03-16 | Evc Technology Ag | Vinyl chloride production process |
| WO1995007249A1 (en) * | 1993-09-07 | 1995-03-16 | Evc Technology Ag | Oxychlorination process |
| US5763710A (en) * | 1993-09-07 | 1998-06-09 | Evc Technology Ag | Oxychlorination process |
| US6180841B1 (en) | 1994-10-20 | 2001-01-30 | Evc Technology Ag | Single stage fixed bed oxychlorination of ethylene |
| US6797845B1 (en) | 1999-11-22 | 2004-09-28 | Dow Global Technologies Inc. | Process for vinyl chloride manufacture from ethane and ethylene with immediate HCl recovery from reactor effluent |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6680415B1 (en) | 1999-11-22 | 2004-01-20 | Dow Global Technologies Inc. | Oxyhalogenation process using catalyst having porous rare earth halide support |
-
1982
- 1982-06-21 GB GB08217898A patent/GB2101596B/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995007251A1 (en) * | 1993-09-07 | 1995-03-16 | Evc Technology Ag | Vinyl chloride production process |
| WO1995007249A1 (en) * | 1993-09-07 | 1995-03-16 | Evc Technology Ag | Oxychlorination process |
| US5728905A (en) * | 1993-09-07 | 1998-03-17 | Evc Technology Ag | Vinyl chloride production process |
| US5763710A (en) * | 1993-09-07 | 1998-06-09 | Evc Technology Ag | Oxychlorination process |
| CN1046930C (en) * | 1993-09-07 | 1999-12-01 | Evc技术公开股份有限公司 | Oxychlorination process |
| US6180841B1 (en) | 1994-10-20 | 2001-01-30 | Evc Technology Ag | Single stage fixed bed oxychlorination of ethylene |
| US6797845B1 (en) | 1999-11-22 | 2004-09-28 | Dow Global Technologies Inc. | Process for vinyl chloride manufacture from ethane and ethylene with immediate HCl recovery from reactor effluent |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2101596B (en) | 1985-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5053493B2 (en) | Process for converting ethylene to vinyl chloride and novel catalyst compositions useful for the process | |
| KR100886284B1 (en) | Oxidative Halogenation and Optional Dehydrogenation of C3+ Hydrocarbons | |
| US4300005A (en) | Preparation of vinyl chloride | |
| US6821924B2 (en) | Oxyhalogenation process using catalyst having porous rare earth halide support | |
| US5202511A (en) | Catalyst diluent for oxychlorination process | |
| JP3566320B2 (en) | Catalyst composition | |
| US3670037A (en) | Catalyst system | |
| US6909024B1 (en) | Process for the conversion of ethylene to vinyl chloride and novel catalyst compositions useful for such process | |
| AU2002307548A1 (en) | Oxidative halogenation and optional dehydrogenation of C3+ hydrocarbons | |
| US4100211A (en) | Process for preparation of ethylene and vinyl chloride from ethane | |
| JPS61225141A (en) | Manufacture of ethane and ethylene | |
| GB2101596A (en) | Oxychlorination of alkanes to monochlorinated olefins | |
| US4375569A (en) | Process for the oxychlorination of an alkane using a solid solution catalyst containing iron cations | |
| KR100283791B1 (en) | Process for producing acrylic acid from acrolein by redox reaction and use of solid mixed oxide composition as redox system in the reaction | |
| US3746737A (en) | Ammoxidation of saturated hydrocarbons | |
| CA1072532A (en) | Process for the oxychlorination of an alkane using a solid solution catalyst containing iron cations | |
| GB2095242A (en) | Preparation of monochloro- olefins by oxychlorination of alkanes | |
| US3799998A (en) | Manufacture of halogenated hydrocarbons | |
| CA1116587A (en) | Oxyhalogenation process | |
| US5334789A (en) | Oxychlorination catalyst process for preparing the catalyst and method of oxychlorination with use of the catalyst | |
| US3454663A (en) | Oxychlorination using a deacon catalyst supported on alumina alpha-monohydrate | |
| US4467127A (en) | Process for the oxychlorination of an alkane using a solid solution catalyst containing iron cations | |
| US4461919A (en) | Process for the oxychlorination of an alkane using a solid solution catalyst containing iron cations | |
| CA1111454A (en) | Preparation of vinyl chloride | |
| US4415757A (en) | Production of saturated carbonyl compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |