US1945960A - Production of hydrocarbons - Google Patents
Production of hydrocarbons Download PDFInfo
- Publication number
- US1945960A US1945960A US516829A US51682931A US1945960A US 1945960 A US1945960 A US 1945960A US 516829 A US516829 A US 516829A US 51682931 A US51682931 A US 51682931A US 1945960 A US1945960 A US 1945960A
- Authority
- US
- United States
- Prior art keywords
- per cent
- hydrocarbons
- methane
- weight
- employed
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/02—Apparatus characterised by their chemically-resistant properties
- B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
- B01J2219/0277—Metal based
- B01J2219/0286—Steel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S585/00—Chemistry of hydrocarbon compounds
- Y10S585/929—Special chemical considerations
- Y10S585/943—Synthesis from methane or inorganic carbon source, e.g. coal
Definitions
- This invention relates to improvements in the utacture and production of hydrocarbons from gaseous or vaporous hydrocarbons of the methane series.
- Unsaturated hydrocarbons such as ethylene, propylene and the like, may be readily converted into valuable liquid hydrocarbons, such as benzone and benzine, without any injurious deposition of carbon by employing as catalysts heavy metals of group 1 of the periodic system, namely gold, silver or copper or alloys of gold, silver or copper, as for example brass, (bronze, manganesecopper or alloys of gold or silver with copper, or-a coherent heat-resistant metal such as iron, copper or alloys such as V2A steel or the like which has been coated with tin, zinc, lead, aluminium or chromium, especially in such a form that the said catalysts exhibit more or less coherent surfaces.
- heavy metals of group 1 of the periodic system namely gold, silver or copper or alloys of gold, silver or copper, as for example brass, (bronze, manganesecopper or alloys of gold or silver with copper, or-a coherent heat-resistant metal such as iron, copper or alloys such as V2A steel or the like which has been coated with
- the said metallic coatings are preferably is embedded in metal powder.
- the said metallic materials can also be employed in .a very advantageous mannerfor the thermal conversion of gaseous or vaporous hydrocarbons of the methane series and more particularly the homologues of methane into other hydrocarbons, especially into oleflnes, such as ethylene, propylene, butylene and the like, or into liquid hydrocarbons, especially liquid aromatic hydrocarbons.
- the said metallic materials are advantageously employed as a constructional material for the apparatus.
- the said con version is carried out in the presence of the above mentioned metallic substances with particular advantage when employing free elementary silicon as a catalyst. Commercial silicon may also be employed. 'So much silicon'should always be present in the catalyst that even if some of it enter into combination, free elementary silicon is always present.
- Metals such as iron or copper may be present in the silicon and it may be employed on non-metallic carriers.
- the catalyst is employed in a molded form it is advantageous to prepare it from silicon powder by incorporating therewith non-metallic binding agents such as clay, or other aluminium silicates, or alumina if desired with an addition of metals.
- non-metallic binding agents such as clay, or other aluminium silicates, or alumina if desired with an addition of metals.
- the temperatures required example is converted at lower temperatures than methane.
- a gas containing large amounts of hydrocarbons requires lower temperatures than a gas containing only small amounts thereof.
- reaction products may be very considerably influenced by the temperature and the duration of the treatment.
- a relatively high temperature for example of .more than 700 C. and a short period of heating
- the gaseous initial hydrocarbons are converted into liquid hydrocarbons under nor- 1 mal conditions of temperature and pressure.
- These products consist mainly of aromatic and gasoline-like products and they boil mainly below 200 C. They are admirably suited for employment as non-knocking motor fuels or as 1141- 9 temperatures of between 500 and 700 C. and a 700 C. for a length of centimetres.
- Example 1 l0 litres of a gas having the compositlon 6.16
- Example 3 C. for 60 centimetres o; its length.
- the hydrocarbons employed are converted, so that (calculated with Example 4 8 litres of a gas mixture containing sulphur compounds and consisting 01' about '76 per cent by volume of the methane homologues, ethane,
- propane and butane, 10 per cent of methane, 4 per cent of hydrogen, 8 to 9 per-cent of nitrogen and about 1 to 2 percent of hydrogen sulphide-"ls passed hourly. through a tube having an internal diameter of 20 millimetres and heated over a length of 60 centimetres to a temperature of about 800 C.
- liquid products About 67.2 homologues are converted into liquid products,,30 per cent by weight into methane and 2.5 to 2.8- per cent by weight into gaseous oleflnes. About '10 per cent by weight oi! the liquid hydrocarbons obtained boil at a temperature up to 200 C.
- These 12 consist to the extent 0t 60 to '70 percent of arcmatic hydrocarbons or low boiling point, such as benzene, toluene and xylene, to the extent 01 2 to v 5 per cent of styrene and the remainder of allphatic hydrocarbons o1 low boiling point.
- the liquid products of higher boiling point consist almost exclusively of unsaturated hydrocarbons which are very well suited for. the production 01 lubricating oils of high viscosity.
- the low boiling reaction products are good'motor i'uelsr What we claim is:.
- a process for the production of oleflnes which comprises passing a gas comprising butane, propane and ethane through an internally tinned manganese-copper tube, which is heated to about 700 C.
- a process for the conversion of an impure hydrocarbon of the methane series containing sulphur into more valuable hydrocarbons which comprises treating said hydrocarbon of the meth- 4 ane series at a temperature between 360 and 900 C. and in. the presence of a heatresistant heavy metal of group l of the periodic'system and 01' free elementary silicon.
- a process for the conversion or an impure hydrocarbon of the methane series containing sulphur into more valuable hydrocarbons which comprises treating said hydrocarbon of the methane series at a temperature between 360 and 900 C. and in the presence or an alloy of a heat-* per cent by weight'of the methane ill resistant heavy metal 01' group 1 of the periodic 900 C. and in the presence of a heat resistant system and of free elementary silicon.
- a process for the conversion of an impure hydrocarbon of the methane series containing sulphur into more valuable hydrocarbons which comprises treating said hydrocarbon of the methane series at a temperature between 360 and CERTIFICATE i CORRECTION.
- Patent No. l, 945, 960 Patent No. l, 945, 960.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Feb. 6, 1934 OFFICE 1,945,960 raonuo'non or nrnnocaanons Fritz Winkier and Hans liaeuber, Ludwigshafenon-the-lthine, Germany No Drawing. Application February is, 1931', Serial No. 516,829, and in Germany February 4 Claims.
This invention relates to improvements in the utacture and production of hydrocarbons from gaseous or vaporous hydrocarbons of the methane series.
Unsaturated hydrocarbons, such as ethylene, propylene and the like, may be readily converted into valuable liquid hydrocarbons, such as benzone and benzine, without any injurious deposition of carbon by employing as catalysts heavy metals of group 1 of the periodic system, namely gold, silver or copper or alloys of gold, silver or copper, as for example brass, (bronze, manganesecopper or alloys of gold or silver with copper, or-a coherent heat-resistant metal such as iron, copper or alloys such as V2A steel or the like which has been coated with tin, zinc, lead, aluminium or chromium, especially in such a form that the said catalysts exhibit more or less coherent surfaces.
The said metallic coatings are preferably is embedded in metal powder.
In this manner between the surfaces of the coating metal and of the metal to be coated an alloy of the two metals is usually formed.
We have now found that the said metallic materials can also be employed in .a very advantageous mannerfor the thermal conversion of gaseous or vaporous hydrocarbons of the methane series and more particularly the homologues of methane into other hydrocarbons, especially into oleflnes, such as ethylene, propylene, butylene and the like, or into liquid hydrocarbons, especially liquid aromatic hydrocarbons. The said metallic materials are advantageously employed as a constructional material for the apparatus. The said con version is carried out in the presence of the above mentioned metallic substances with particular advantage when employing free elementary silicon as a catalyst. Commercial silicon may also be employed. 'So much silicon'should always be present in the catalyst that even if some of it enter into combination, free elementary silicon is always present. Metals such as iron or copper may be present in the silicon and it may be employed on non-metallic carriers.
If the catalyst is employed in a molded form it is advantageous to prepare it from silicon powder by incorporating therewith non-metallic binding agents such as clay, or other aluminium silicates, or alumina if desired with an addition of metals. The temperatures required example, is converted at lower temperatures than methane. A gas containing large amounts of hydrocarbons requires lower temperatures than a gas containing only small amounts thereof.
When working under elevated pressures lower temperatures are necessary than at ordinary pressure. Temperatures ranging between 360 and 900 C.'have proved satisfactory. I
Although generally speaking very high temperatures are necessary for this conversion at which hitherto the danger of deposition of carbon was considerable in many cases, only a .very slight deposition of carbon or none at all takes place on the said materials even when working for long periods of time. Moreover, the said materials promote the conversion catalytically to a very great extent.
In many cases it is sufllcient to construct the walls of the reactionchamber of the said materials. Y
As examples of the hydrocarbons which may be converted in accordance with the present invention may be mentioned methane itself or the homologues thereof, such as ethane, propane and butane. Gas mixtures containing these may also be mentioned such as natural gas, waste gases of the destructive hydrogenation of carbonaceous materials such as tars, mineral oils and the like employed.
It is by no means necessary to purify the 1111- .90
' tial materials from sulphur compounds contained therein, as was necessary when working in the f apparatus hitherto employed, but when treating materials containing sulphur, it is necessary to employ as the metal substratum to which the metallic coating is applied a metal or alloy which is not attacked by sulphur, such as V2A steel or other chromium nickel steels.
The nature of the reaction products may be very considerably influenced by the temperature and the duration of the treatment. Thus by employing a relatively high temperature, for example of .more than 700 C. and a short period of heating, the gaseous initial hydrocarbons are converted into liquid hydrocarbons under nor- 1 mal conditions of temperature and pressure. These products consist mainly of aromatic and gasoline-like products and they boil mainly below 200 C. They are admirably suited for employment as non-knocking motor fuels or as 1141- 9 temperatures of between 500 and 700 C. and a 700 C. for a length of centimetres.
short period of heating are employed highly unsaturated liquid hydrocarbons are produced from vaporized hydrocarbons. These said liquid products are particularly well suited for employment as initial materials in the production-of lubricating oils. d I
The following examples will turther. illustrate the nature of this invention, but the invention is not restricted to these examples. The percentmixture at about 1200 C. By a single passage of the gases 90 per cent by weight of the methane 'homologues contained inthe initial gases are ages are by volume. unless otherwise stated.
Example 1 l0 litres of a gas having the compositlon 6.16
per cent by volume of butylene, 37.84 per cent.
by volume of butane, 4.5 per cent by volume of propylene, 39.5 per cent by volume of propane, 0.84 per cent by volume of ethylene and 11.16 per cent by volume of ethane are passed per hour at ordinary pressure through a copper tube 18 millimetres in internal diameter and 60 centimetres in length heated to 800 C. 18 litres of a gas containing 4.0 per cent by volume of hutylenes and propylenes and 31.0'per cent oi. ethylene are obtained perhour. Furthermore, 130 cubic centimetres of liquid hydrocarbons, which consist mainly of benzene, are obtained per cubic metre oi the gas mixture employed. After working for several days the copper tube is still entirely free from carbon. At higher temperatures the yield of) liquid hydrocarbons, especially of benzene, is still higher, and naphthalene and anthracene are also formed.
",Erample 2 4.8 lltres oia gas mixture containing 32.5 per cent of butane, 34 per cent of propane, 9.5 per cent of ethane, 8.4 per cent of higher olefines,
. 0.8 per cent of ethylene and 14.8 per cent of nitrogen are passed per hour through an internally tinned manganese copper tube 18 millimetres ininternal diameter which is heated to After passing thesaid mixture through once a mixture of hydrocarbons, containing 60 per cent by volumeoi oleflnes which in turn contain 67 per cent of ethylene, is obtained. Deposits of car- I bon cannot be detected'atter working for several days.
Example 3 C. for 60 centimetres o; its length. By one pas-' sage 94 per cent by-weight oi the hydrocarbons employed are converted, so that (calculated with Example 4 8 litres of a gas mixture containing sulphur compounds and consisting 01' about '76 per cent by volume of the methane homologues, ethane,
propane and butane, 10 per cent of methane, 4 per cent of hydrogen, 8 to 9 per-cent of nitrogen and about 1 to 2 percent of hydrogen sulphide-"ls passed hourly. through a tube having an internal diameter of 20 millimetres and heated over a length of 60 centimetres to a temperature of about 800 C. The said tube is made of V2A steel and is provided internally with a homogeneous coating of'lead. It is filled with uniform spherold lumps of about the size of peas prepared from silicon powder by molding with a binding agent such as clay and heating the converted. Reckoned on the total initial gases. 25 per cent by weight are converted into ethylene and 30 per centby weight into liquid prod ucts boiling above 40 C. "and consisting of -a1i= phatic and aromatic hydrocarbons: Carbon is 05.
notdeposited in the tube. I
' Example 5 2 cubic metres oi'a gas consisting of 11.5 per cent by weight of 'olefines. 6.5 per cent by weight 100.
of-methane, 81.8 per cent by weight of methane homologues and about 0.2 per cent by weight of hydrogen sulphide are passed under a pressure of 50 atmospheres'through'a tube 5 metres'long-L "same direction as the direction of flow-of the gases.
About 67.2 homologues are converted into liquid products,,30 per cent by weight into methane and 2.5 to 2.8- per cent by weight into gaseous oleflnes. About '10 per cent by weight oi! the liquid hydrocarbons obtained boil at a temperature up to 200 C. These 12 consist to the extent 0t 60 to '70 percent of arcmatic hydrocarbons or low boiling point, such as benzene, toluene and xylene, to the extent 01 2 to v 5 per cent of styrene and the remainder of allphatic hydrocarbons o1 low boiling point. The liquid products of higher boiling point consist almost exclusively of unsaturated hydrocarbons which are very well suited for. the production 01 lubricating oils of high viscosity. The low boiling reaction products are good'motor i'uelsr What we claim is:.
1. A process for the production of oleflnes, which comprises passing a gas comprising butane, propane and ethane through an internally tinned manganese-copper tube, which is heated to about 700 C. I
2. A process for the conversion of an impure hydrocarbon of the methane series containing sulphur into more valuable hydrocarbons, which comprises treating said hydrocarbon of the meth- 4 ane series at a temperature between 360 and 900 C. and in. the presence of a heatresistant heavy metal of group l of the periodic'system and 01' free elementary silicon.
3. A process for the conversion or an impure hydrocarbon of the methane series containing sulphur into more valuable hydrocarbons, which comprises treating said hydrocarbon of the methane series at a temperature between 360 and 900 C. and in the presence or an alloy of a heat-* per cent by weight'of the methane ill resistant heavy metal 01' group 1 of the periodic 900 C. and in the presence of a heat resistant system and of free elementary silicon.
4. A process for the conversion of an impure hydrocarbon of the methane series containing sulphur into more valuable hydrocarbons, which comprises treating said hydrocarbon of the methane series at a temperature between 360 and CERTIFICATE i CORRECTION.
Patent No. l, 945, 960.
February 6, 1934.
FRITZ WINKLER, AL.
It is hereby certified that the above numbered patent was erroneously issued to the inventors said "Winkler-andHaeuber" whereas. said Letters Patent should have been issued to I. G. Farbenindustrie Aktiengesellschaft, Frankfort-on-the-Main, Germany, as assignee ofthe entire interest in said invention, as shown by the records of assignments in this office; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.
Signed and sealed this 3rd day of April, A. D. 1934.
(Seal) F. M. Hopkins Acting Commissioner of Patents.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1945960X | 1930-02-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
US1945960A true US1945960A (en) | 1934-02-06 |
Family
ID=7750733
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US516829A Expired - Lifetime US1945960A (en) | 1930-02-20 | 1931-02-18 | Production of hydrocarbons |
Country Status (1)
Country | Link |
---|---|
US (1) | US1945960A (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1064496B (en) * | 1956-03-07 | 1959-09-03 | Bayer Ag | Process for the dehydrogenation of hydrocarbons |
US3223743A (en) * | 1961-12-29 | 1965-12-14 | Monsanto Chemicals | Dehydrogenation of ethylbenzene |
US3244760A (en) * | 1962-11-19 | 1966-04-05 | Dow Chemical Co | Method for cracking aliphatic hydrocarbons |
US3247276A (en) * | 1962-07-09 | 1966-04-19 | Texaco Inc | Catalytic treatment of hydrocarbons |
US4507517A (en) * | 1983-10-31 | 1985-03-26 | Chevron Research Company | Conversions of low molecular weight hydrocarbons to higher molecular weight hydrocarbons using a boron compound containing catalyst |
US4567311A (en) * | 1983-10-31 | 1986-01-28 | Chevron Research Company | Conversions of low molecular weight hydrocarbons to higher molecular weight hydrocarbons using a silicon compound-containing catalyst |
US4599474A (en) * | 1983-10-31 | 1986-07-08 | Chevron Research Company | Conversions of low molecular weight hydrocarbons to higher molecular weight hydrocarbons using a metal-containing catalyst |
US4822944A (en) * | 1986-07-11 | 1989-04-18 | The Standard Oil Company | Energy efficient process for upgrading light hydrocarbons and novel oxidative coupling catalysts |
US4929789A (en) * | 1988-01-15 | 1990-05-29 | The Standard Oil Company | Process for pyrolyzing or thermal cracking a gaseous or vaporized hydrocarbon feedstock using a novel gas-solids contacting device and an oxidation catalyst |
US5012028A (en) * | 1986-07-11 | 1991-04-30 | The Standard Oil Company | Process for upgrading light hydrocarbons using oxidative coupling and pyrolysis |
US5066629A (en) * | 1989-06-30 | 1991-11-19 | The Broken Hill Proprietary Company Limited | Oxidative coupling catalyst for methane |
-
1931
- 1931-02-18 US US516829A patent/US1945960A/en not_active Expired - Lifetime
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1064496B (en) * | 1956-03-07 | 1959-09-03 | Bayer Ag | Process for the dehydrogenation of hydrocarbons |
US3223743A (en) * | 1961-12-29 | 1965-12-14 | Monsanto Chemicals | Dehydrogenation of ethylbenzene |
US3247276A (en) * | 1962-07-09 | 1966-04-19 | Texaco Inc | Catalytic treatment of hydrocarbons |
US3244760A (en) * | 1962-11-19 | 1966-04-05 | Dow Chemical Co | Method for cracking aliphatic hydrocarbons |
US4507517A (en) * | 1983-10-31 | 1985-03-26 | Chevron Research Company | Conversions of low molecular weight hydrocarbons to higher molecular weight hydrocarbons using a boron compound containing catalyst |
US4567311A (en) * | 1983-10-31 | 1986-01-28 | Chevron Research Company | Conversions of low molecular weight hydrocarbons to higher molecular weight hydrocarbons using a silicon compound-containing catalyst |
US4599474A (en) * | 1983-10-31 | 1986-07-08 | Chevron Research Company | Conversions of low molecular weight hydrocarbons to higher molecular weight hydrocarbons using a metal-containing catalyst |
US4822944A (en) * | 1986-07-11 | 1989-04-18 | The Standard Oil Company | Energy efficient process for upgrading light hydrocarbons and novel oxidative coupling catalysts |
US5012028A (en) * | 1986-07-11 | 1991-04-30 | The Standard Oil Company | Process for upgrading light hydrocarbons using oxidative coupling and pyrolysis |
US4929789A (en) * | 1988-01-15 | 1990-05-29 | The Standard Oil Company | Process for pyrolyzing or thermal cracking a gaseous or vaporized hydrocarbon feedstock using a novel gas-solids contacting device and an oxidation catalyst |
US5066629A (en) * | 1989-06-30 | 1991-11-19 | The Broken Hill Proprietary Company Limited | Oxidative coupling catalyst for methane |
US5132481A (en) * | 1989-06-30 | 1992-07-21 | The Broken Hill Proprietary Company Limited | Process of methane oxidative coupling with hydrogen activation of catalyst |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2063596A (en) | Thermal treatment of carbon compounds | |
US1945960A (en) | Production of hydrocarbons | |
NO136648B (en) | ||
US1847095A (en) | Prevention of the formation of carbon in operations carried out with hydrocarbons at an elevated temperature | |
US2168840A (en) | Inhibiting carbon formation in metal reaction vessels | |
Zhang et al. | Mechanism and kinetics of n-butane dehydrogenation to 1, 3-butadiene catalyzed by isolated Pt sites grafted onto≡ SiOZn–OH nests in dealuminated zeolite Beta | |
US3484499A (en) | Catalytic disproportionation of paraffinic hydrocarbons | |
US2379670A (en) | Removal of acetylene from gases | |
SU434660A3 (en) | METHOD OF CATALYTIC GASIFICATION OF HYDROCARBONS | |
US1949109A (en) | Reaction with hydrogen and in apparatus therefor | |
US2045794A (en) | Conversion of liquid carbonaceous materials of high boiling point range | |
US1541175A (en) | Process for producing styrol and its homologues from aromatic hydrocarbons | |
US1868127A (en) | Production of valuable hydrocarbons | |
US2411236A (en) | Method of converting hydrocarbons into organic sulphur compounds | |
US1842010A (en) | Gesellschaft | |
US2973384A (en) | Process for synthesizing ethylene | |
US1365849A (en) | Process of producing aromatic hydrocarbons | |
US3466159A (en) | Process and catalyst for production of methane-rich gas | |
US3248441A (en) | High temperature hydrocarbon reactions | |
KR20200111210A (en) | Method and apparatus for methylation of toluene and benzene in aromatic complexes | |
Taniewski et al. | Hydropyrolysis of hydrocarbons | |
US2002534A (en) | Method for the production of normally liquid hydrocarbons from gaseous or lower boiling hydrocarbon materials | |
US3641191A (en) | Method for reduction of polymer formation in a process for converting ethylene to alpha olefins | |
US1894255A (en) | Production of liquid hydrocarbons from olefines | |
US2339106A (en) | Production of motor fuels |