US2117022A - Conversion of hydrocarbons - Google Patents
Conversion of hydrocarbons Download PDFInfo
- Publication number
- US2117022A US2117022A US705237A US70523734A US2117022A US 2117022 A US2117022 A US 2117022A US 705237 A US705237 A US 705237A US 70523734 A US70523734 A US 70523734A US 2117022 A US2117022 A US 2117022A
- Authority
- US
- United States
- Prior art keywords
- hydrocarbons
- radicals
- conversion
- temperature
- higher boiling
- 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
- 229930195733 hydrocarbon Natural products 0.000 title description 31
- 150000002430 hydrocarbons Chemical class 0.000 title description 27
- 238000006243 chemical reaction Methods 0.000 title description 19
- 238000009835 boiling Methods 0.000 description 26
- 238000000034 method Methods 0.000 description 15
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical group CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 12
- -1 hydrocarbon radicals Chemical class 0.000 description 11
- 150000003254 radicals Chemical class 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
- Y10S585/942—Production of carbonium ion or hydrocarbon free-radical
Definitions
- This invention relates to the conversion of hydrocarbons, particularly thoseof the unsaturated aliphatic type into hydrocarbons of higher boiling points. It is well-known that considerable quantities of unsaturated hydrocarbons, especially those of the olefin series, are commercially available as raw materials and it is the primary object of the invention to provide a method whereby such materials may be converted into 10 more valuable products such as lubricating oils or fuels of high quality.
- hydrocarbons of lower boiling points may be polymerized or otherwise converted into hydrocarbons of higher boiling points by subjecting them to suitable temperatures and pressures in the presence of alkyl or aryl radicals.
- the hydrocarbon radicals preferably alkyl radicals such as methyl, ethyl, butyl and the like, are preferably introduced into the reaction chamber by direct decomposition of metal comcompounds.
- the activity of the reaction or the yield of converted products is greatly affected by the phase of the reacting materials and I find it highly desirable to maintain the materials in the liquid phase. This may be accomplished by the presence of a solvent, which may, itself, be relatively inert, and which is liquid at the temperatures and pressures employed. This may, however, be supplied at least in part by theproducts of conversion. Hydrocarbons which will remain liquid at the temperatures and pressures involved are suitable solvents. Benzene and naphthalene may be usedas inert solvents.
- the temperature employed may be relatively low as compared with the temperatures required for usual cracking processes preferably not above approximately 300 C.
- the principal consideration is that the temperature be suflicient to cause decomposition of the metal alkyl employed as a source of the alkyl radicals.
- a temperature of 180 C. is suificient to cause decomposition of tetraethyl lead and temperatures in general not exceeding approximately 275 (2,..have been found quite suflicient in carrying 'o1 1t the process with ethylene as the raw material and tetraethyl lead as the source of the activating radicals.
- Relatively low temperatures are especially desirable because cracking with the resultant formation of carbon and other undesirable products may thereby be avoided.
- the pressure to be employed is largely depend ent upon the materials used, and, in a static or batch procedure, will vary with the progress of pounds of the radicals such as lead or mercury the reaction.
- the principal consideration is to maintain a high concentration of the reacting hydrocarbons in relation to the activating radicals.
- the pressure desirable will be related to the vapor pressure of the materials and the temperature should be maintained below the critical temperature of the solvent.
- the choice of the metal compound depends upon several factors, one being commercial availability. So far as the conditions of the process are concerned, there are two principal considerations, one being the temperature at which the compound decomposes to yield the radicals and the other being the character of the residual substance. This residue should preferably be inert and readily separable from the desirable end products. For this reason the lead and mercury aikyls are especially recommended, although other metal alkyl and aryl compounds decomposable at relatively low temperatures have been found operable.
- the endproduct will depend also upon the raw material since higher boiling olefins, such as heptene, will be converted into higher boiling products than will the lower boiling olefins, such as ethylene, other conditions being equaL.
- higher boiling olefins such as heptene
- ethylene other conditions being equaL.
- One marked advantage in the process is that the product is remarkably free from undesirable constituents, being according to my experience, a colorless oil capable of being fractionated to yield engine fuels of high anti-knock properties and lubricating oils of excellent quality.
- tetraethyl lead was added to 0.684 mol. of ethylene in 50 c. c. of benzene in a reaction bomb.
- the bomb was subjected to a temperature not exceeding approximately 275 C., for about four hours during which the pressure reached a maximum of 1900 lbs. per square inch.
- About of the ethylene was converted to a colorless oil.
- drocarbons from hydrocarbons of lower boiling points comprising heating said lower boiling hydrocarbons in the liquid phase in the presence of a hydrocarbon compound of a metal of the class consisting of lead and mercury, said compound being one which upon heating decomposes to yield ahydrocarbon radical, said radicals combining with the said lower boiling hydrocarbon and promoting polymerization and conversion thereof to yield higher boiling hydrocarbons.
- the temperature ofthe reacting mixture being sufflcient to effect liberation of hydrocarbon radicals from said compound and below that at which material cracking effects will occur.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Description
Patented May 10, 1938 PATENT OFFICE CONVERSION F HYDROCARBONS Paul L. Cramer, Highland Park, Mich, assignor, by mesne assignments, to General'Motors Corporation, Detroit, Mich., a corporation of Delaware No Drawing.
Application January 4, 1934,
Serial No. 705,237
8 Claims.
This invention relates to the conversion of hydrocarbons, particularly thoseof the unsaturated aliphatic type into hydrocarbons of higher boiling points. It is well-known that considerable quantities of unsaturated hydrocarbons, especially those of the olefin series, are commercially available as raw materials and it is the primary object of the invention to provide a method whereby such materials may be converted into 10 more valuable products such as lubricating oils or fuels of high quality.
I have found that hydrocarbons of lower boiling points may be polymerized or otherwise converted into hydrocarbons of higher boiling points by subjecting them to suitable temperatures and pressures in the presence of alkyl or aryl radicals. The hydrocarbon radicals, preferably alkyl radicals such as methyl, ethyl, butyl and the like, are preferably introduced into the reaction chamber by direct decomposition of metal comcompounds.
The activity of the reaction or the yield of converted products is greatly affected by the phase of the reacting materials and I find it highly desirable to maintain the materials in the liquid phase. This may be accomplished by the presence of a solvent, which may, itself, be relatively inert, and which is liquid at the temperatures and pressures employed. This may, however, be supplied at least in part by theproducts of conversion. Hydrocarbons which will remain liquid at the temperatures and pressures involved are suitable solvents. Benzene and naphthalene may be usedas inert solvents.
The temperature employed may be relatively low as compared with the temperatures required for usual cracking processes preferably not above approximately 300 C. The principal consideration is that the temperature be suflicient to cause decomposition of the metal alkyl employed as a source of the alkyl radicals. For example, a temperature of 180 C., is suificient to cause decomposition of tetraethyl lead and temperatures in general not exceeding approximately 275 (2,..have been found quite suflicient in carrying 'o1 1t the process with ethylene as the raw material and tetraethyl lead as the source of the activating radicals. Relatively low temperatures are especially desirable because cracking with the resultant formation of carbon and other undesirable products may thereby be avoided.
The pressure to be employed is largely depend ent upon the materials used, and, in a static or batch procedure, will vary with the progress of pounds of the radicals such as lead or mercury the reaction. The principal consideration is to maintain a high concentration of the reacting hydrocarbons in relation to the activating radicals. The pressure desirable will be related to the vapor pressure of the materials and the temperature should be maintained below the critical temperature of the solvent.
The reactions which take place. are apparently quite complex and go beyond a mere combination of the radicals derived from the metal compound with the hydrocarbon used as a raw material, since a relatively small amount of the metal compound brings about the conversion of a relatively great quantity of .the hydrocarbon. It appears that the action of the radicals is in a sense catalytic in that they are to a large extent regenerated in the progress of the reaction and again become available to activate further chain formations in the hydrocarbon molecules. A certain proportion of the radicals do, however, become combined or become inactive in the product so that a continuous process will require the constant addition of smallquantities of the metal compound. 7
The choice of the metal compound depends upon several factors, one being commercial availability. So far as the conditions of the process are concerned, there are two principal considerations, one being the temperature at which the compound decomposes to yield the radicals and the other being the character of the residual substance. This residue should preferably be inert and readily separable from the desirable end products. For this reason the lead and mercury aikyls are especially recommended, although other metal alkyl and aryl compounds decomposable at relatively low temperatures have been found operable.
The time during which the reaction may be continued will ailect the product, a longer time resulting in a higher proportion of high boiling constituents.
The endproduct will depend also upon the raw material since higher boiling olefins, such as heptene, will be converted into higher boiling products than will the lower boiling olefins, such as ethylene, other conditions being equaL. One marked advantage in the process is that the product is remarkably free from undesirable constituents, being according to my experience, a colorless oil capable of being fractionated to yield engine fuels of high anti-knock properties and lubricating oils of excellent quality.
A similar reaction occurs with some of the saturated paraffin and hydrogenated aromatic hydrocarbons. For example, I have obtained over 30% of'conversion in the treatment of ndecane, and as high as in the treatment of tetralin.
As a specific example of a demonstration of the process, 0.0005 mol. of tetraethyl lead was added to 0.684 mol. of ethylene in 50 c. c. of benzene in a reaction bomb. The bomb was subjected to a temperature not exceeding approximately 275 C., for about four hours during which the pressure reached a maximum of 1900 lbs. per square inch. About of the ethylene was converted to a colorless oil.
I claim:
1. The process of producing higher boiling hy-.
drocarbons from hydrocarbons of lower boiling points comprising heating said lower boiling hydrocarbons in the liquid phase in the presence of a hydrocarbon compound of a metal of the class consisting of lead and mercury, said compound being one which upon heating decomposes to yield ahydrocarbon radical, said radicals combining with the said lower boiling hydrocarbon and promoting polymerization and conversion thereof to yield higher boiling hydrocarbons. the temperature ofthe reacting mixture being sufflcient to effect liberation of hydrocarbon radicals from said compound and below that at which material cracking effects will occur.
2. Process as in claim 1, the upper limit of temperature being approximately 300 C. and the said compound being a metal alkyl.
3. Process as in claim 1, the lower boiling hydrocarbons being oleflnic.
4. The process of producing higher boiling oils from hydrocarbons of lower boiling points comprising heating said lower boiling hydrocarbons in the liquid phase to temperatures not substantially in excess of 300 C. in the presence of a catalyst, said catalyst being an alkyl compound oi a metal from the group consisting of lead and mercury and acting to promote polymerization and conversion of said lower boiling hydrocarbons to yield hydrocarbons of higher boiling points.
5. Process as set forth in claim-4, the lower boiling hydrocarbons being olefinic.
6. The process of producing higher boiling oils comprising heating a liquid mixture containing ethylene and a metal alkyl to a temperature sufllcient to decompose the metal alkyl thereby freeing alkyl radicals which combine with ethylene and promote its conversion to higher boiling hydrocarbons, said metal being one of the class consisting of lead and mercury.
7. The process of producing higher boiling oils from ethylene comprising heating a liquid mixture containing ethylene and tetraethyl lead to a temperature sufiicient to decompose the tetraethyl lead to free hydrocarbon radicals from the tetraethyl lead, said radicals combining with the ethylene and promoting ,conversion thereof to higher boiling hydrocarbons.
' 8. The process of producing higher boiling oils from olefinic hydrocarbons of lower boiling points comprising preparing a mixture of the said hydrocarbons and a solvent therefor, adding to said mixture a compound of a hydrocarbon radical and a metal of the class consisting of lead and mercury, heating the mixture to a temperature sufficient to decompose the metal compound to yield the hydrocarbon radical and maintaining the temperature below the critical temperature of the solvent, the freed radicals combining with the said olefins and promoting polymerization and conversion thereof to yield higher boiling hydrocarbons suitable for fuels and lubricating oils.
PAUL L. CRAMER.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US705237A US2117022A (en) | 1934-01-04 | 1934-01-04 | Conversion of hydrocarbons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US705237A US2117022A (en) | 1934-01-04 | 1934-01-04 | Conversion of hydrocarbons |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2117022A true US2117022A (en) | 1938-05-10 |
Family
ID=24832603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US705237A Expired - Lifetime US2117022A (en) | 1934-01-04 | 1934-01-04 | Conversion of hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2117022A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2435760A (en) * | 1942-03-14 | 1948-02-10 | Pure Oil Co | Thermal conversion of hydrocarbons promoted by explosive organic nitrogen compounds |
| US2500161A (en) * | 1948-08-14 | 1950-03-14 | Socony Vacuum Oil Co Inc | Conversion of 1-olefins in the presence of lead tetraacetate |
| US2502444A (en) * | 1945-03-12 | 1950-04-04 | Houdry Process Corp | Production of high molecular weight elastic hydrocarbon polymers in the presence of lead tetraethyl |
| US2695327A (en) * | 1950-06-21 | 1954-11-23 | Ziegler Karl | Dimerization of unsaturated hydrocarbons |
| US3072631A (en) * | 1955-11-29 | 1963-01-08 | Eastman Kodak Co | Polymerization of alpha-olefins with three component soluble catalysts in liquid phase |
| US3094573A (en) * | 1961-04-13 | 1963-06-18 | Sun Oil Co | Preparation of methyl pentenes |
| US3182096A (en) * | 1960-09-02 | 1965-05-04 | British Petroleum Co | Dimerisation of propylene |
-
1934
- 1934-01-04 US US705237A patent/US2117022A/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2435760A (en) * | 1942-03-14 | 1948-02-10 | Pure Oil Co | Thermal conversion of hydrocarbons promoted by explosive organic nitrogen compounds |
| US2502444A (en) * | 1945-03-12 | 1950-04-04 | Houdry Process Corp | Production of high molecular weight elastic hydrocarbon polymers in the presence of lead tetraethyl |
| US2500161A (en) * | 1948-08-14 | 1950-03-14 | Socony Vacuum Oil Co Inc | Conversion of 1-olefins in the presence of lead tetraacetate |
| US2695327A (en) * | 1950-06-21 | 1954-11-23 | Ziegler Karl | Dimerization of unsaturated hydrocarbons |
| US3072631A (en) * | 1955-11-29 | 1963-01-08 | Eastman Kodak Co | Polymerization of alpha-olefins with three component soluble catalysts in liquid phase |
| US3182096A (en) * | 1960-09-02 | 1965-05-04 | British Petroleum Co | Dimerisation of propylene |
| US3094573A (en) * | 1961-04-13 | 1963-06-18 | Sun Oil Co | Preparation of methyl pentenes |
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