US2912475A - Manufacture of low molecular unsaturated hydrocarbons - Google Patents
Manufacture of low molecular unsaturated hydrocarbons Download PDFInfo
- Publication number
- US2912475A US2912475A US578581A US57858156A US2912475A US 2912475 A US2912475 A US 2912475A US 578581 A US578581 A US 578581A US 57858156 A US57858156 A US 57858156A US 2912475 A US2912475 A US 2912475A
- Authority
- US
- United States
- Prior art keywords
- gas
- oxygen
- carrier gas
- temperature
- stream
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/35—Formation of carbon-to-carbon triple bonds only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/78—Processes with partial combustion
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/36—Controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
- C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
Definitions
- the hot combustion gases from an oxyhydrogen flame are used as a carrier; these gases are mixed in a nozzle with a hydrocarbon that is gaseous at room temperature andunder normal pressure, and the mixture of gases is chilled after a short time of reaction.
- this process involves the disadvantage that thevhot combustion gases of the oxyhydrogen flame contain a considerable proportion of oxygen-containing radicals, oxygen atoms and oxygen molecules which react with part of the hydro carbon to form carbon monoxide and carbon dioxide.
- Our present invention provides a process for the manufacture of low molecular unsaturated aliphatic hydrocarbons, especially acetylene and/or ethylene, in which a hydrocarbon containing at least two carbon atoms is pyrolized by contacting it for a short time with a carrier gas consisting of hot combustion gas containing hydrogen, wherein the oxygenand oxygen-containing radicals, oxygen atoms and oxygen molecules which are formed by dissociation and-are contained in the hot combustion gas are first recombined by the introduction of at least one secondary gas having a lower temperature than the combustion gas and which is advantageously of the same chemical nature as the combustion gas,
- the amount of the hydrocarbon introduced is so selected that the temperature of the gas mixture still amounts to at least 700 C. after the gas has been mixed and reacted with the hydrocarbon and prior to the chilling of the reaction mixture obtained.
- hydrocarbons there are used aliphatic hydrocarbons.
- hydrocarbons which are liquid at room temperature there can advantageously be used any hydrocarbons, such as hexanes, he'ptanes, octanes, decanes, the mono-unsaturated aliphatic hydrocarbons, commercial mixtures of hydrocarbons, such as petroleum distillates, fractions of benz'ine, topped oils, diesel oils etc.
- the process according to this invention can be conducted with particular advantage without application of superatmospheric pressure. It is, however, also possible toperform the pyrolysis both with application of elevated pressure or under sli htly reduced pressure.
- Ascarrier gas there maybe used with advantage the combustion-gases of oils, coal dust, gaseous hydrocarbons, hydrogen, etc. to which freehydrogen is added, if not yet contained in these compounds.
- As' carrier gas there may also be used mixtures of hydrogen with steam and carbon monoxide, if desired in admixture with carbon dioxide or small amounts of other-substances which do not affect the reaction and as obtained by combustion of the aforesaid substances orAby-the addition of hydrogen.
- carrier gas nitrogen or carbon dioxide alone or gas mixtures rich in nitrogen or carbon dioxide.
- secondary gases there may also be used the gases that are formed by the combustion of the substances described in the preceding paragraph.
- steam it has proved to be particularly advantageous to use steam as carrier gas, and to use steam and/or hydrogen as secondary gas.
- the hydrogen can be introduced into the carrier gas at any temperature desired; if, however, steam is used as a secondary gas, such steam is required to have a temperature which at least corresponds to the boiling point of the water under the corresponding pressure.
- mixtures of steam or mixtures of steam and hydrogen it is, however, advantageous to introduce these mixtures at a temperature of at least 150 C.
- the quantity of the secondary gas used may vary within wide limits; furthermore, the amount is dependent on the temperature of the carrier gas and the secondary gas.
- the amount of the secondary gas used generally, amounts to bet-ween 1 and 80 percent by weight, preferably 30 to 70 percent by weight, and is in each case calculated upon the sum of carrier gas and secondary gas.
- the hydrocarbon is introduced according to methods known per se; it is preferable to introduce the hydrocarbons at a temperature not in excess of 400 C., so that no cracking occurs prior to the reaction. It is, however, also possible to introduce liquid hydrocarbons by injection.
- the carrier gas is produced, as has already been mentioned above, by combustion of a combustible substance immediately before contacting the hydrocarbon.
- a nozzle is arranged between the combustion flame and the reaction chamber, it being of advantage to mix the hydrocarbon with the gas used as carrier gas immediately behind that nozzle.
- the propellant has a temperature of about 2200" C. and, when it is mixed with said hydrocarbons, a temperature of about 1650 C. At 2200" C. there are still present noteworthy quantities of oxygencontaining radicals, oxygen atoms and oxygen molecules which favour the formation of carbon monoxide from the hydrocarbons to be reacted.
- the gases to be reacted are preheated on the filling material to temperatures of about 1000 C. and more prior to being mixed up, whereby distinct cracking occurs.
- This process is very complicated and can only be conducted, if at all, with the use of hydrocarbons which are gaseous at room temperature because of the high temperatures required for pre-heating and owing to the special mode of pre-heating the aforesaid hydrocarbons which are to be reacted; this pre-heating operation involves pumping the cooled filling material into a second container to be heated up.
- EXAMPLE 1 (A) To the hot combustion gases obtained by'combustion, per hour, of 26 normal cubic metres (cubic metreat 0 C. under atmospheric pressure) of hydrogen and 12 normal cubic metres of oxygen, ethylene is added in an amount such that the temperature in the reaction zone is about 1100 to 1300 C. The gases are reacted within about 0.005 second and then chilled.
- EXAMPLE 4 Under the conditions applied in Example 3 are reacted the same amounts of hydrogen, oxygen and hydrocarbons of the same petroleum fraction (boiling range: 54360 C.) with the exception, however, that the combustion gases are mixed, per hour, with 19.5 kilograms of steam prior to being mixed up with the hydrocarbons.
- a process for the manufacture of low molecular weight unsaturated aliphatic hydrocarbons which comprises (a) forming a stream of hot combustion gas containing oxygen atoms, oxygen molecules and oxygencontaining radicals formed by dissociation; (b) introducing a secondary gas into said stream of hot combustion gas for recombining the oxygen atoms, oxygen molecules and oxygen-containing radicals therein and thereby form-' ing a stream of carrier gas which is substantially free from molecular oxygen and contains hydrogen, said secondary gas having a temperature of at least about 150 C. but a lower temperature than the combustion gas and the amount thereof being about 1 to 80% by weight,
- a process for the manufacture of low molecular weight unsaturated aliphatic hydrocarbons rich in unsaturated C hydrocarbons which comprises (a) forming a stream of hot combustion gas obtained by combustion of an excess of hydrogen with oxygen and containing oxygen atoms, oxygen molecules and oxygen-containing radicals formed by dissociation; (b) introducing a secondary gas into said stream of hot combustion gas for recombining the oxygen atoms, oxygen molecules and oxygen-containing radicals therein and thereby forming a stream of carrier gas which is substantially free from molecular oxygen and contains hydrogen, said secondary gas being selected from the group consisting of hydrogen, steam and mixtures thereof and having a temperature of at least about 150 C.
- a process for the manufacture of low molecular weight unsaturated aliphatic hydrocarbons rich in acetylene which comprises (a) forming a stream of hot combustion gas obtained by combustion of an excess of hydrogen with oxygen and containing oxygen atoms, oxygen molecules and oxygen-containing radicals formed by dissociation; (b) introducing a secondary gas into said stream of hot combustion gas for recombining the oxygen atoms, oxygen molecules and oxygen-containing radicals therein and thereby forming a stream of carrier gas which is substantially free from molecular oxygen and contains hydrogen, said secondary gas being selected from the group consisting of hydrogen, steam and mixtures thereof and having a temperature of at least about 150 C.
- a process according to claim 1, wherein the hydrocarbon to be pyrolized is liquid at room temperature and g is contacted with the combustion gas in the geaseous state.
- a combustion gas which consists substantially of a mixture of steam, hydrogen and carbon monoxide.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Combustion & Propulsion (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF17423A DE1114182B (de) | 1955-04-28 | 1955-04-28 | Verfahren zur Herstellung von Acetylen und gegebenenfalls AEthylen enthaltenden Gasgemischen |
Publications (1)
Publication Number | Publication Date |
---|---|
US2912475A true US2912475A (en) | 1959-11-10 |
Family
ID=7088578
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US578581A Expired - Lifetime US2912475A (en) | 1955-04-28 | 1956-04-17 | Manufacture of low molecular unsaturated hydrocarbons |
Country Status (5)
Country | Link |
---|---|
US (1) | US2912475A (sk) |
BE (1) | BE547407A (sk) |
DE (1) | DE1114182B (sk) |
FR (1) | FR1161043A (sk) |
GB (1) | GB823956A (sk) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3019271A (en) * | 1958-09-08 | 1962-01-30 | Belge Produits Chimiques Sa | Process and apparatus for treatment of hydrocarbons |
US3116344A (en) * | 1960-08-19 | 1963-12-31 | Shell Oil Co | Vortex tube reactor and process for converting hydrocarbons therein |
US3116343A (en) * | 1960-08-19 | 1963-12-31 | Shell Oil Co | Temperature-stabilized conversion of hydrocarbons and the like |
US3129266A (en) * | 1961-09-11 | 1964-04-14 | Messrs Kogyokaihatsu | Process for production of acetylene by thermal decomposition of hydrocarbons |
US3180904A (en) * | 1959-05-15 | 1965-04-27 | Hoechst Ag | Process for the manufacture of olefins |
US3240836A (en) * | 1960-06-21 | 1966-03-15 | Hoechst Ag | Process for cracking hydrocarbons |
US3270076A (en) * | 1965-10-28 | 1966-08-30 | Nat Lead Co | Propylene cracking |
US4206032A (en) * | 1978-03-17 | 1980-06-03 | Rockwell International Corporation | Hydrogenation of carbonaceous materials |
US4256565A (en) * | 1979-11-13 | 1981-03-17 | Rockwell International Corporation | Method of producing olefins from hydrocarbons |
US4536603A (en) * | 1983-12-22 | 1985-08-20 | Rockwell International Corporation | Production of acetylene from coal by contact with a combustion gas |
US4724272A (en) * | 1984-04-17 | 1988-02-09 | Rockwell International Corporation | Method of controlling pyrolysis temperature |
US11123705B1 (en) | 2018-10-23 | 2021-09-21 | Sabic Global Technologies B.V. | Method and reactor for conversion of hydrocarbons |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA835434A (en) * | 1964-11-09 | 1970-02-24 | Happel John | Pyrolysis of hydrocarbons |
GB1504776A (en) * | 1975-08-14 | 1978-03-22 | Davy Powergas Ltd | Hydrocracking c3 or higher hydrocarbon feedstock |
EP0059772B1 (en) * | 1981-03-09 | 1985-12-04 | The Dow Chemical Company | Crude oil cracking using partial combustion gases |
JPS59152992A (ja) * | 1983-02-18 | 1984-08-31 | Mitsubishi Heavy Ind Ltd | 炭化水素からオレフインを製造するための熱分解法 |
JPS59159887A (ja) * | 1983-03-03 | 1984-09-10 | Mitsubishi Heavy Ind Ltd | 炭化水素からオレフインを製造するための熱分解法 |
JPS6011585A (ja) * | 1983-06-30 | 1985-01-21 | Mitsubishi Heavy Ind Ltd | 炭化水素から石油化学製品を製造するための熱分解法 |
JPS6011584A (ja) * | 1983-06-30 | 1985-01-21 | Mitsubishi Heavy Ind Ltd | 炭化水素から石油化学製品を選択的に製造するための熱分解法 |
US4982039A (en) * | 1987-09-03 | 1991-01-01 | University Of Southern California | Conversion of halogenated toxic substances |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2371147A (en) * | 1945-03-13 | Preparation op unsaturated ali | ||
US2520149A (en) * | 1944-06-14 | 1950-08-29 | Koppers Co Inc | Process for producing olefins |
US2706210A (en) * | 1950-12-05 | 1955-04-12 | Wulff Process Company | Process suitable for converting primary hydrocarbons to secondary hydrocarbons |
US2767233A (en) * | 1952-01-07 | 1956-10-16 | Chemical Construction Corp | Thermal transformation of hydrocarbons |
US2816941A (en) * | 1953-11-27 | 1957-12-17 | Phillips Petroleum Co | Production of unsaturated hydrocarbons and apparatus therefor |
US2823243A (en) * | 1956-03-19 | 1958-02-11 | Phillips Petroleum Co | Process and apparatus for pyrolysis of hydrocarbons |
-
0
- BE BE547407D patent/BE547407A/xx unknown
-
1955
- 1955-04-28 DE DEF17423A patent/DE1114182B/de active Pending
-
1956
- 1956-04-17 US US578581A patent/US2912475A/en not_active Expired - Lifetime
- 1956-04-18 GB GB11859/56A patent/GB823956A/en not_active Expired
- 1956-04-27 FR FR1161043D patent/FR1161043A/fr not_active Expired
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2371147A (en) * | 1945-03-13 | Preparation op unsaturated ali | ||
US2520149A (en) * | 1944-06-14 | 1950-08-29 | Koppers Co Inc | Process for producing olefins |
US2706210A (en) * | 1950-12-05 | 1955-04-12 | Wulff Process Company | Process suitable for converting primary hydrocarbons to secondary hydrocarbons |
US2767233A (en) * | 1952-01-07 | 1956-10-16 | Chemical Construction Corp | Thermal transformation of hydrocarbons |
US2816941A (en) * | 1953-11-27 | 1957-12-17 | Phillips Petroleum Co | Production of unsaturated hydrocarbons and apparatus therefor |
US2823243A (en) * | 1956-03-19 | 1958-02-11 | Phillips Petroleum Co | Process and apparatus for pyrolysis of hydrocarbons |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3019271A (en) * | 1958-09-08 | 1962-01-30 | Belge Produits Chimiques Sa | Process and apparatus for treatment of hydrocarbons |
US3180904A (en) * | 1959-05-15 | 1965-04-27 | Hoechst Ag | Process for the manufacture of olefins |
US3240836A (en) * | 1960-06-21 | 1966-03-15 | Hoechst Ag | Process for cracking hydrocarbons |
US3116344A (en) * | 1960-08-19 | 1963-12-31 | Shell Oil Co | Vortex tube reactor and process for converting hydrocarbons therein |
US3116343A (en) * | 1960-08-19 | 1963-12-31 | Shell Oil Co | Temperature-stabilized conversion of hydrocarbons and the like |
US3129266A (en) * | 1961-09-11 | 1964-04-14 | Messrs Kogyokaihatsu | Process for production of acetylene by thermal decomposition of hydrocarbons |
US3270076A (en) * | 1965-10-28 | 1966-08-30 | Nat Lead Co | Propylene cracking |
US4206032A (en) * | 1978-03-17 | 1980-06-03 | Rockwell International Corporation | Hydrogenation of carbonaceous materials |
US4256565A (en) * | 1979-11-13 | 1981-03-17 | Rockwell International Corporation | Method of producing olefins from hydrocarbons |
FR2469446A1 (fr) * | 1979-11-13 | 1981-05-22 | Rockwell International Corp | Procede de production rapide d'olefines par conversion thermique d'hydrocarbures en presence d'hydrogene |
US4536603A (en) * | 1983-12-22 | 1985-08-20 | Rockwell International Corporation | Production of acetylene from coal by contact with a combustion gas |
US4724272A (en) * | 1984-04-17 | 1988-02-09 | Rockwell International Corporation | Method of controlling pyrolysis temperature |
US11123705B1 (en) | 2018-10-23 | 2021-09-21 | Sabic Global Technologies B.V. | Method and reactor for conversion of hydrocarbons |
Also Published As
Publication number | Publication date |
---|---|
GB823956A (en) | 1959-11-18 |
DE1114182B (de) | 1961-09-28 |
BE547407A (sk) | |
FR1161043A (fr) | 1958-08-19 |
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