US2317603A - Utilization of petroleum refinery gas - Google Patents
Utilization of petroleum refinery gas Download PDFInfo
- Publication number
- US2317603A US2317603A US223760A US22376038A US2317603A US 2317603 A US2317603 A US 2317603A US 223760 A US223760 A US 223760A US 22376038 A US22376038 A US 22376038A US 2317603 A US2317603 A US 2317603A
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- United States
- Prior art keywords
- gasoline
- boiling
- gas
- hydrocarbons
- utilization
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- 239000003208 petroleum Substances 0.000 title description 8
- 239000007789 gas Substances 0.000 description 23
- 238000009835 boiling Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 15
- 239000003502 gasoline Substances 0.000 description 13
- 229930195733 hydrocarbon Natural products 0.000 description 11
- 150000002430 hydrocarbons Chemical class 0.000 description 11
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000000446 fuel Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 235000013844 butane Nutrition 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
Images
Classifications
-
- 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
- C10G7/00—Distillation of hydrocarbon oils
Definitions
- Patented Apr. 27, 1943 2,317,803 I UTILIZATION OF rggi tomum REFINERY Eric B. Hjerpe, Port Arthur, Tex., and William A.
- This invention relates to utilization of petroleum refinery gas; and it comprises a process wherein a petroleum refinery gas containing butylenes is fractionated to separate a fraction containing only butylenes and constituents slightly higher boiling than butylenes, wherein the fraction so separated is subjected to a temperature and a pressure sufiicient to polymerize the butylenes and other components of the fraction to products having a boiling point within the range of gasoline boiling points; all as more fully hereinafter set forth and as claimed.
- butylenes may be separated from the bulk of refinery gases together with components of approximately the same boiling point range and the entire fraction so separated utilized to great advantage by subjecting it to polymerization. We have found that such polymerization, when properly controlled,
- a refinery gas containing butylenes is subjected to fractionation to recover therefrom a fraction containing the butylenes together with other components of nearly the same boiling point range such as the butanes.
- This 04 cut may be removed from the bulk of the refinery gases by any of several methods, such as fractional liquefaction of the gas or by more or less complete liquefaction followed by fractional distillation, etc. Advanta'geously, a method is chosen which best fits in with the independent treatment of other of the gas constituents such as the amylenes, propane, and
- the C4 cut is subjected to controlled temperatures and pressures sufficient to cause polymerization of some or all of its components with the ultimate production of a liquid polymer boiling within the range of gasoline boiling points. If polymerization is carried too far, the product is too high boiling and if not carried far enough, the yield becomes unprofitable.
- the velocity of polymerization varies directly as the temperature and directly as the pressure according to known chemical laws. That is to say, for a given velocity of reaction, if the pressure is raised, the temperature may be lowered; and if the temperature is raised, the pressure may be lowered.
- reference character I indicates a stream of starting stock which may be, for instance, the gases from a "stabilizer or- "debutanizer in which raw pressure distillate or compression gasoline is weathered or stabilized. These gases are sometimes termed debutanizer gas. They comprise largely the aliphatic hydrocarbons of the C4 group and usually contain varying amounts of butane-1, butene-2, and isobutene as well as butanes.
- Stream l enters a compressor 2 wherein it is subjected to any pressure desired during subsequent operations. From the compressor 2, the stream l is conveyed through a heater il wherein the constituents are brought to the desired'temperature.
- the stream Leaving the heater, the stream enters either valved line 4 leading to a catalyst chamber 5 or valved by-pass line. f circumventing the catalyst chamber.
- Catalyst chamber 5 is located in a temperature maintaining chamber I by means of which the temperature of the catalyst chamber may be controlled within narrow limits.
- the stream of polymerized material Leaving the catalyst chamber 5, or by-pass line 6, the stream of polymerized material enters a condenser 9 wherein the products of polymerization are cooled. From condenser 9, the products are transferred through line In and pump II to a fractionating tower i2 where the products are subjected to any desired fractionation and the permanent gases removed.
- Tower I2 is equipped for removal of various fractions as side streams.
- the gas is heated to a temperature of 350 C. and polymerized, after which the products are conveyed directly to the condenser 9 through by-pass line 6.
- the invention is not to be considered as limited with regard to any particular way of fractionating the polymer produced.
- the figure simply illustrates an advantageous way of finishing the unfractionated product.
Description
April 27, 1943. E. B. HJERPE ET AL 2,317,603
UTILIZATION OF PETROLEUM REFINERY GAS Original Filed March 25, 1936 COMPRESSOR Q 1 ll HEATER, 4 W 5 cozvoszvsze PUMP CHAMBER 7 DE) GAS 70 TEMPERAfi/I? 72 CONTROL LOW BOILING I NAPHTHA TEMPERATURE g CONT EOL.
I (xii/norm GASOLINA jwu coal/046 11 7 T1301? .li je fie, VVi Zl mmfl Gruse,
Patented Apr. 27, 1943 2,317,803 I UTILIZATION OF rggi tomum REFINERY Eric B. Hjerpe, Port Arthur, Tex., and William A.
Gruse, Wilkinsbnrg, Pa., assign era to Gulf Oil Corporation, Pittsburgh, Pa., a corporation of Pennsylvania Original application March 25, 1936, Serial No. 70,856. Divided and this application August 8, 1938, Serial No. 223,760
2 Claims. (Cl. 196-10) This invention relates to utilization of petroleum refinery gas; and it comprises a process wherein a petroleum refinery gas containing butylenes is fractionated to separate a fraction containing only butylenes and constituents slightly higher boiling than butylenes, wherein the fraction so separated is subjected to a temperature and a pressure sufiicient to polymerize the butylenes and other components of the fraction to products having a boiling point within the range of gasoline boiling points; all as more fully hereinafter set forth and as claimed.
The present application is a division of our prior copending application Serial No. 70,856, filed March 25, 1936, which is in part a continuation of our prior application Serial No. 613,774, filed May 26, 1932, now U. S. Patent No. 2,099,480, patented November 16, 1937.
In the cracking of petroleum, decomposition occurs with the formation of components of less complexity from those of greater complexity. In addition, saturated hydrocarbons are converted into unsaturates. Most petroleum cracking is directed toward the formation of gasoline, but decomposition products are invariably formed which are too low boiling to be included in commercially acceptable gasoline.
Among the decomposition products arising from the cracking of petroleum are the aliphatic hydrocarbons having four carbon atoms. Large quantities of butylenes are produced, and on.
account of the low boiling point and high vola tility of this fraction, in many cases the butylenes cannot be retained in the gasoline fraction; large quantities of the butylenes must therefore be allowed to'escape as free gas or used as fuel.
We have discovered that the butylenes may be separated from the bulk of refinery gases together with components of approximately the same boiling point range and the entire fraction so separated utilized to great advantage by subiecting it to polymerization. We have found that such polymerization, when properly controlled,
will yield products boiling within the gasoline boiling point range and, in addition, such products will be characterized by remarkably high anti-knocking tendencies. The products are useful either alone as special fuel or for blending with other gasoline to decrease the knocking characteristics of the latter.
According to our invention, a refinery gas containing butylenes is subjected to fractionation to recover therefrom a fraction containing the butylenes together with other components of nearly the same boiling point range such as the butanes. We term this the C4 cut." This 04 cut may be removed from the bulk of the refinery gases by any of several methods, such as fractional liquefaction of the gas or by more or less complete liquefaction followed by fractional distillation, etc. Advanta'geously, a method is chosen which best fits in with the independent treatment of other of the gas constituents such as the amylenes, propane, and
propylene, etc. Such a method is described in our parent application serial No. 613,774 wherein part of the C4 cut is obtained as an overhead from gasoline condensed under pressure, while the remainder is obtained as a liquid residue after removal of lower boiling fractions from a liquefied light fraction of gas.
In accordance with one embodiment of the invention,-the C4 cut is subjected to controlled temperatures and pressures suficient to cause polymerization of some or all of its components with the ultimate production of a liquid polymer boiling within the range of gasoline boiling points. If polymerization is carried too far, the product is too high boiling and if not carried far enough, the yield becomes unprofitable. Within limits, the velocity of polymerization varies directly as the temperature and directly as the pressure according to known chemical laws. That is to say, for a given velocity of reaction, if the pressure is raised, the temperature may be lowered; and if the temperature is raised, the pressure may be lowered.
In the absence of catalysts, we find that convenient conditions under which to polymerize the C4 out are temperatures of about 350 C. and pressures sumcient to cause the reaction to Proceed at a practical velocity which, at the stated temperature, would be approximately 1000 lbs. per square inch. Much lower pressures may be used if desired, but at the stated temperature the reaction proceeds somewhat more slowly. This may be compensated for, at least in part, by raising the temperature. We find that polymerization may be readily accomplished at temperatures under 350 6., although the velocity of reaction is less. Again we may compensate for this by increasing the pressure.
The accompanying drawing illustrates diagrammatically a specific embodiment of the invention. In the drawing, the single figure is a fiow sheet illustrating process steps for thermal polymerization, in accordance with our invention.
Referring to the drawing, reference character I indicates a stream of starting stock which may be, for instance, the gases from a "stabilizer or- "debutanizer in which raw pressure distillate or compression gasoline is weathered or stabilized. These gases are sometimes termed debutanizer gas. They comprise largely the aliphatic hydrocarbons of the C4 group and usually contain varying amounts of butane-1, butene-2, and isobutene as well as butanes. Stream l enters a compressor 2 wherein it is subjected to any pressure desired during subsequent operations. From the compressor 2, the stream l is conveyed through a heater il wherein the constituents are brought to the desired'temperature. Leaving the heater, the stream enters either valved line 4 leading to a catalyst chamber 5 or valved by-pass line. f circumventing the catalyst chamber. Catalyst chamber 5 is located in a temperature maintaining chamber I by means of which the temperature of the catalyst chamber may be controlled within narrow limits. Leaving the catalyst chamber 5, or by-pass line 6, the stream of polymerized material enters a condenser 9 wherein the products of polymerization are cooled. From condenser 9, the products are transferred through line In and pump II to a fractionating tower i2 where the products are subjected to any desired fractionation and the permanent gases removed. Tower I2 is equipped for removal of various fractions as side streams. Accurate control of the fractionation is facilitated by temperature control elements l3, I4- and i5. .Advantageousaly, we control the temperatures within the tower 12 so as to remove at one level a product of motor gasoline boiling range and to remove at another level a lower boiling product suitable for use as a blending naphtha. Any material boiling over the gasoline range may be withdrawn through line I6, and residual gases leave the tower through conduit I1. Our process is usually so conducted as to produce a minimum of residual gases and a minimum of polymers higher boiling than gasoline. The low boiling naphtha removed as a side stream is of high octane number and makes an excellent product for blending with motor fuels of lower octane number andof lower volatility. The motor gasoline is likewise of high octane number and may be used as a special premium motor fuel or as a blending agent for raising the antiknock characteristics of other gasolines.
In the heater coil 3 the gas is heated to a temperature of 350 C. and polymerized, after which the products are conveyed directly to the condenser 9 through by-pass line 6.
The invention is not to be considered as limited with regard to any particular way of fractionating the polymer produced. The figure simply illustrates an advantageous way of finishing the unfractionated product.
Others in the prior art have proposed to subject various gaseous hydrocarbons and gas fractions to high temperatures, in excess of 1200 F.,
to crack the same and occasionally (when long times of contact are employed) to produce aromatic oils, such as benzol and toluol. Such op erations are sometimes referred to as "polymerizing" operations, although the terms "gas Pyrolysis" and gas cracking are to .be preferred. In any event, our process does not contemplate the use of such temperatures, which are neither necessary nor desirable when converting gases predominating in butane and butylene to gasoline-like hydrocarbons, as distinguished from aromatics.
Weare also aware that it has been proposed to polymerize various olefin-containing gases, or pure olefins, at temperatures between about 200 and 400 0., in the presence of oxygen. Our invention does not however contemplate the use of oxygen for the deliberate purpose of affecting the reactions taking place, nor is such use intended to becovered by the term "polymerization" as employed herein.
What we claim is:
I. In the manufacture of gasoline-like hydrocarbons of high anti-knock value when used as motor fuel, from normally gaseous hydrocarbons produced in cracking petroleum oils by subjecting such normally gaseous hydrocarbons in the absence of a catalyst to elevated temperatures and pressures effective to polymerize normally gaseous constituents to low-boiling, normally liquid products, the improvement which comprises subjecting a fraction consisting predominantly of saturated and unsaturated hydrocarbons having four carbon atoms per molecule, containing relatively small amounts of hydrocarbons having three carbon atoms per molecule but substantially free from more refractory hydrocarbons such as methane, ethane and ethylene, to a polymerizing temperature of the order of 350 C. and a pressure of about 1000 pounds per square inch.
2. In the manufacture of gasoline-like hydrocarbons of high anti-knock value when used as motor fuel, from normally gaseous hydrocarbons such as those produced in cracking petroleum oils, by subjecting such normally gaseous hydrocarbons in the absence of a catalyst to elevated temperatures and pressures effective to polymerize normally gaseous constituents to low-boiling, normally liquid products, the improvement which comprises subjecting to said polymerizing temperatures and pressures a fraction consisting predominantly of saturated and unsaturated hydrocarbons having four carbon atoms per molecule, containing relatively small amounts of hydrocarbons having three carbon atoms per molecule, but
. substantially free from more refractory hydro- ERIC B. HJERPE. WILLIAM A. GRUSE.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US223760A US2317603A (en) | 1936-03-25 | 1938-08-08 | Utilization of petroleum refinery gas |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US7085636A | 1936-03-25 | 1936-03-25 | |
US223760A US2317603A (en) | 1936-03-25 | 1938-08-08 | Utilization of petroleum refinery gas |
Publications (1)
Publication Number | Publication Date |
---|---|
US2317603A true US2317603A (en) | 1943-04-27 |
Family
ID=26751558
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US223760A Expired - Lifetime US2317603A (en) | 1936-03-25 | 1938-08-08 | Utilization of petroleum refinery gas |
Country Status (1)
Country | Link |
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US (1) | US2317603A (en) |
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1938
- 1938-08-08 US US223760A patent/US2317603A/en not_active Expired - Lifetime
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