US1654821A - Process for the chlorination of saturated hydrocarbons - Google Patents
Process for the chlorination of saturated hydrocarbons Download PDFInfo
- Publication number
- US1654821A US1654821A US717891A US71789124A US1654821A US 1654821 A US1654821 A US 1654821A US 717891 A US717891 A US 717891A US 71789124 A US71789124 A US 71789124A US 1654821 A US1654821 A US 1654821A
- Authority
- US
- United States
- Prior art keywords
- chlorination
- hydrochloric acid
- oxygen
- methane
- liters
- 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.)
- Expired - Lifetime
Links
- 238000005660 chlorination reaction Methods 0.000 title description 18
- 238000000034 method Methods 0.000 title description 13
- 229930195734 saturated hydrocarbon Natural products 0.000 title description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 50
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 20
- 229930195733 hydrocarbon Natural products 0.000 description 16
- 150000002430 hydrocarbons Chemical class 0.000 description 16
- 239000007789 gas Substances 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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
Definitions
- BRICK KRAUSE AN D ROI-OMAN .BOKA, OF KONSTAN Z, GERMANY, A SSIGNOBS TO HOLZ- VEBKOHLUNGB-TNDUSTRIE AKTIEN-GESELLSCHAI'T, F KONSTAN Z, BADE NIA', GER- MANY, A CORPORATION OF GERMANY.
- hydrochloric acid can be brought to reaction with hydrocarbons of the methane group at higher temperatures chlorine substitution products such as CH Cl, CH Cl CHGI being formed.
- Convenient reaction temperatures are for instance those between approximately 300 C. and approximately 650 C. but preferably those between approximately 450C. and 550 C. Temperatures which essentially exceed 650 C. must generally be avoided as they lead to undesired oxidation of the hydrocarbon.
- the process can be carried out in absence of catalysts. It .has however been found advantageous to provide for the pres- 85 ence of such catalysts which favor the oxidation of the hydrochloric acid and, if possible, at the same time the chlorination of the hydrocarbon.
- catalysts which favor the oxidation of the hydrochloric acid and, if possible, at the same time the chlorination of the hydrocarbon.
- both conditions are satisfied by such substances, which are known as promoting chlorination, for instance carbon, cupric chloride, ferric chloride, thallic chloride, the chlorides of the alkaline earths and of the rare earths.
- the presence of such cata- 4 lysts allows the desired oxidation of the hydrochloric acid to take place at comparatively low temperatures, while on the other hand it favors the desired chlorination but not the undesired oxidation of the hydrocarbons.
- the ratio of the reaction components it depends on the working method and on the desired reaction products.
- the oxygen for instance may be applied in the theoretically required quantity. Frequently however it will be advisable to use a suitable excess of oxygen preferably not too large.
- the chlorination according to the invention may also be carried through in presence of diluting means, e. g. in presence of steam. Consequently it is possible to i use aqueous hydrochloric acid instead of hydrogen chloride.
- Oxygen-containing gases for instance air, may replace oxygen.
- E wamples 1 At about 500 C. a mixture of 25 liters of methane,-12 liters of oxygen, 12 liters of hydrochloric acid and liters of steam (corresponding to grams of aqueous hydrochloric acid of 30%) per hour is conducted through a tube of 30 mm. inner diameter heated over a. length of 600 mm., the tube being filled, with grains of fire brick prepared with cupric chloride. 63 92; of the hydrochloric acid introduced is converted to chlorination products of the methane, only ti 1 of the methane used is burnt to carbonic acid.
- the utilization of the hydrochloric acid may be considerably increased, notwithstanding lower temperature, by which burning of the methane on a larger scale is avoided.
- 12 liters of methane, 6 liters of oxygen,6 liters ofhydrochloric acid and 27 liters of steam are conducted through per hour.
- til of the hydrochloric acid is converted to chlorination products of methane, the burning of methane to carbon dioxide not exceeding 5%.
- the hydrochloric acid which is not converted and the unchanged portion of, the hydrocarbon may be used for new charges.
- Methane may be used pure or mixed with other gases, for instance, as marsh gas or natural gas which contains sometimes also considerable quantities of homologues of methane, as gas from distillations, as gas from coke ovens or the like.
- Process for the chlorination of saturated hydrocarbons consisting in causing the said hydrocarbons to react wlth hydrochloric acid and oxygen at temperatures of 300 C. to (550 C., the quantity of oxygen employed and the velocity of the gases being such that the oxidation of the hydrocarbon is avoided.
Description
Patented Jan. 3, 1928.
UNITED STATES PATENT OFFICE.
BRICK KRAUSE AN D ROI-OMAN .BOKA, OF KONSTAN Z, GERMANY, A SSIGNOBS TO HOLZ- VEBKOHLUNGB-TNDUSTRIE AKTIEN-GESELLSCHAI'T, F KONSTAN Z, BADE NIA', GER- MANY, A CORPORATION OF GERMANY.
PROCESS FOR THE CHLOBINA'I'ION OF SATUBATED HYDBDCABBONS.
30 Drawing. Application filed June 4, 1924, Serial No. 717,891, and in Germany November 14, 1928.
By recent publications it is known that hydrochloric acid acts upon non-saturated ali hatic hydrocarbons with formation of ad itive products. All experiments intending to bring to reaction saturated hydrocarbons with hydrochloric acid have however failed up to the present.
We have found that, in the presence of oxygen, hydrochloric acid can be brought to reaction with hydrocarbons of the methane group at higher temperatures chlorine substitution products such as CH Cl, CH Cl CHGI being formed.
According to the well known facts, it was to be expected that the oxygen would oxidize or burn the hydrocarbon at the high temperatures necessary for carrying through the process. Our experiments however have shown, that it is possible to carry outsubstitution reactions, for instance the reaction,
at elevated temperatures without oxidizing the hydrocarbon. Convenient reaction temperatures are for instance those between approximately 300 C. and approximately 650 C. but preferably those between approximately 450C. and 550 C. Temperatures which essentially exceed 650 C. must generally be avoided as they lead to undesired oxidation of the hydrocarbon.
The process can be carried out in absence of catalysts. It .has however been found advantageous to provide for the pres- 85 ence of such catalysts which favor the oxidation of the hydrochloric acid and, if possible, at the same time the chlorination of the hydrocarbon. We have found that both conditions are satisfied by such substances, which are known as promoting chlorination, for instance carbon, cupric chloride, ferric chloride, thallic chloride, the chlorides of the alkaline earths and of the rare earths. The presence of such cata- 4 lysts allows the desired oxidation of the hydrochloric acid to take place at comparatively low temperatures, while on the other hand it favors the desired chlorination but not the undesired oxidation of the hydrocarbons.
As to the ratio of the reaction components it depends on the working method and on the desired reaction products. The oxygen for instance may be applied in the theoretically required quantity. Frequently however it will be advisable to use a suitable excess of oxygen preferably not too large.
The chlorination according to the invention may also be carried through in presence of diluting means, e. g. in presence of steam. Consequently it is possible to i use aqueous hydrochloric acid instead of hydrogen chloride. Oxygen-containing gases, for instance air, may replace oxygen.
E wamples 1. At about 500 C. a mixture of 25 liters of methane,-12 liters of oxygen, 12 liters of hydrochloric acid and liters of steam (corresponding to grams of aqueous hydrochloric acid of 30%) per hour is conducted through a tube of 30 mm. inner diameter heated over a. length of 600 mm., the tube being filled, with grains of fire brick prepared with cupric chloride. 63 92; of the hydrochloric acid introduced is converted to chlorination products of the methane, only ti 1 of the methane used is burnt to carbonic acid.
2..If in the same tube the gases are introduced with'half the velocity as stated under 1, the utilization of the hydrochloric acid may be considerably increased, notwithstanding lower temperature, by which burning of the methane on a larger scale is avoided. For instance at temperatures between 450 C. and 500 C. 12 liters of methane, 6 liters of oxygen,6 liters ofhydrochloric acid and 27 liters of steam (cor responding to 30 grams of 30% aqueous hydrochloric acid) are conducted through per hour. til of the hydrochloric acid is converted to chlorination products of methane, the burning of methane to carbon dioxide not exceeding 5%.
The charge of methane and hydrochloric acid being reduced by one half according to Example No. 2, the use of air instead of oxygen does not essentially impair the conversion of the hydrochloric acid, the formation of carbonic acid however being slightly reduced. If for instance per hour 12 liters of methane, 30 liters of air, 6 liters of hydrochloric acid and 27 liters of steam at 450 C. to 500 C. are conducted through the same tube, (Ni of the hydrochloric acid is converted to chlorination products, and 4 to 4 parts of carbon dioxide are formed from 100 parts of methane.
4. Working with h drochloric acid gas instead of aqueous hydrochloric acid larger charges easily may be treated. At the same time burning of methane to carbon dioxide may be reduced to a minimum by avoiding the excess of oxygen which in the Examples Nos. 13 amounted to 100%. At 450 C.-
500 C. 12 liters of marsh gas, or natural gas, 12 liters of hydrochloric acid and 6 liters of oxygen per hour being conducted through, 60% of the hydrochloric acid is converted to chlorination products and 2% of the methane to carbon dioxide.
As numerous experiments have shown the losses resulting from the undesired oxidation processes generally never exceed 5% of the introduced hydrocarbon, thus being so low that they are practically of no account. The hydrochloric acid which is not converted and the unchanged portion of, the hydrocarbon may be used for new charges.
As has been described and shown by the examples above it is possible to control the chlorination process in such a manner that the oxygen oxidizes only the hydrochloric acid, but practically does not attack the hydrocarbon to be chlorinated. Theinvention thus permits the production of partially chlorinated products that is those containing hydrogen which are generally most valuable, this result being mainly obtained by avoiding injurious superheating. The use of suitable catalysts allowing the temperature to be lowered, has proved to be very advantageous, as has already been stated above.
Starting from this knowledge experiments make it easily possible to find out in every case the most favorable conditions as to ratio of reacting gases, height of temperature, catalysts, velocity of flow of the reacting gases, dilution means and so on, in order to obtain a good yield of the desired chlorination products.
The method is extraordinarily successful for the chlorination of methane and its homologues. Methane may be used pure or mixed with other gases, for instance, as marsh gas or natural gas which contains sometimes also considerable quantities of homologues of methane, as gas from distillations, as gas from coke ovens or the like.
We claim:
1. Process for the chlorination of saturated hydrocarbons consisting in causing the said hydrocarbons to react wlth hydrochloric acid and oxygen at temperatures of 300 C. to (550 C., the quantity of oxygen employed and the velocity of the gases being such that the oxidation of the hydrocarbon is avoided.
2. Process for the chlorination of saturated hydrocarbons consisting in causing the said hydrocarbons to react with hydrochloric acid and oxygen at temperatures of 300 C. to 650 C. in the presence of a catalyst capable of promoting chlorination, the quantity of oxygen'employed and the velocity of the gases being such that the oxidation of the hydrocarbon is avoided.
3. Process for the chlorination of saturated hydrocarbons consisting in causin the said hydrocarbons to react with hydroch oric acid and oxygen at temperatures of 300 C. to 650 C. in the presence of metallic chlorides as catalysts, the quantity of oxygen employed and the velocity of the gases being such that the oxidation of the hydrocarbon is avoided.
4. Process for the chlorination of methane consisting in causing the same to react with hydrochloric acid and oxygen at temperatures of 300 C. to 650 0., the quantity of oxygen employed and the velocity of the gases being such that the oxidation of the methane is avoided.
5. Process as claimed in claim 4 in which the reaction is eflected in the presence of a catalyst capable of promoting chlorination.
In testimony whereof we aflix our signatures.
ERICH KRAUSE. KOLOMAN ROKA.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1654821X | 1923-11-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1654821A true US1654821A (en) | 1928-01-03 |
Family
ID=7738382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US717891A Expired - Lifetime US1654821A (en) | 1923-11-14 | 1924-06-04 | Process for the chlorination of saturated hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US1654821A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2498546A (en) * | 1946-01-11 | 1950-02-21 | Socony Vacuum Oil Co Inc | Manufacture of halogenated hydrocarbons |
| US2568660A (en) * | 1942-07-16 | 1951-09-18 | Rosen Raphael | Fluorination process |
| US2578913A (en) * | 1949-11-02 | 1951-12-18 | Du Pont | Fluorination of hydrocarbons |
| US2674633A (en) * | 1948-12-07 | 1954-04-06 | Reitlinger Otto | Chlorination of hydrocarbons |
| US2846484A (en) * | 1954-02-02 | 1958-08-05 | Monsanto Chemicals | Production of chlorinated aliphatic compounds |
| US3210431A (en) * | 1960-05-30 | 1965-10-05 | Shell Oil Co | Oxychlorination of ethylene |
| DE1205080B (en) * | 1962-08-24 | 1965-11-18 | Pittsburgh Plate Glass Co | Process for the production of halogenated hydrocarbons |
| US3240827A (en) * | 1961-07-13 | 1966-03-15 | Laine Francois | Process for the oxychlorination of aliphatic hydrocarbons |
| DE1219473B (en) * | 1961-05-16 | 1966-06-23 | Pittsburgh Plate Glass Co | Process for the production of unsaturated chlorinated hydrocarbons with 2 to 4 carbon atoms |
| US3267161A (en) * | 1962-07-26 | 1966-08-16 | Osaka Kinzoku Kogyo Company Lt | Chlorination process |
| DE1222914B (en) * | 1960-09-26 | 1966-08-18 | Pittsburgh Plate Glass Co | Process for the production of trichlorethylene and perchlorethylene |
-
1924
- 1924-06-04 US US717891A patent/US1654821A/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2568660A (en) * | 1942-07-16 | 1951-09-18 | Rosen Raphael | Fluorination process |
| US2498546A (en) * | 1946-01-11 | 1950-02-21 | Socony Vacuum Oil Co Inc | Manufacture of halogenated hydrocarbons |
| US2674633A (en) * | 1948-12-07 | 1954-04-06 | Reitlinger Otto | Chlorination of hydrocarbons |
| US2578913A (en) * | 1949-11-02 | 1951-12-18 | Du Pont | Fluorination of hydrocarbons |
| US2846484A (en) * | 1954-02-02 | 1958-08-05 | Monsanto Chemicals | Production of chlorinated aliphatic compounds |
| US3210431A (en) * | 1960-05-30 | 1965-10-05 | Shell Oil Co | Oxychlorination of ethylene |
| DE1222914B (en) * | 1960-09-26 | 1966-08-18 | Pittsburgh Plate Glass Co | Process for the production of trichlorethylene and perchlorethylene |
| DE1219473B (en) * | 1961-05-16 | 1966-06-23 | Pittsburgh Plate Glass Co | Process for the production of unsaturated chlorinated hydrocarbons with 2 to 4 carbon atoms |
| US3240827A (en) * | 1961-07-13 | 1966-03-15 | Laine Francois | Process for the oxychlorination of aliphatic hydrocarbons |
| US3267161A (en) * | 1962-07-26 | 1966-08-16 | Osaka Kinzoku Kogyo Company Lt | Chlorination process |
| DE1205080B (en) * | 1962-08-24 | 1965-11-18 | Pittsburgh Plate Glass Co | Process for the production of halogenated hydrocarbons |
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