US2340960A - Cycle gas oils by thermal treatment - Google Patents
Cycle gas oils by thermal treatment Download PDFInfo
- Publication number
- US2340960A US2340960A US341813A US34181340A US2340960A US 2340960 A US2340960 A US 2340960A US 341813 A US341813 A US 341813A US 34181340 A US34181340 A US 34181340A US 2340960 A US2340960 A US 2340960A
- Authority
- US
- United States
- Prior art keywords
- oil
- line
- cracking
- thermal treatment
- gas oil
- 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
- 239000003921 oil Substances 0.000 title description 35
- 238000007669 thermal treatment Methods 0.000 title description 6
- 239000007789 gas Substances 0.000 description 18
- 238000005336 cracking Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 238000004523 catalytic cracking Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/10—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with stationary catalyst bed
Definitions
- the present invention relates to the art of treating hydrocarbons. More particularly, the present invention relates to improvements in the catalytic treatment of relatively heavy hydrocarbons such as 'a gas oil to form light fractions boiling within the gasoline range in which the cycle stock, that is to say, the unconverted hydrocarbons recovered from the catalyst zone are subjected to a thermal treatment in order to improve their cracking characteristics or properties.
- relatively heavy hydrocarbons such as 'a gas oil
- the unconverted hydrocarbons recovered from the catalyst zone are subjected to a thermal treatment in order to improve their cracking characteristics or properties.
- a feed stock for a catalytic cracking operation is preferably of a naphthenic character and should also be substantially free of aromatic compounds containing more than one benzene ring in a single condensed nucleus.
- a feed stock used in a catalytic cracking operation contains compounds such as naphthalene, anthracene, phenanthrene, benzenthrene, and the like, or their alkylated derivatives, these condensed ring compounds form during the cracking operation excessive quantities of coke.
- I represents in diagrammatic iorm an apparatus layout or flow diagram in which my perature of 825 F.
- the hot vapors are withdrawn through line 4 and discharged into a catalytic conversion chamber 8 where the vapors contact a catalyst, preferably an acid treated clay catalyst, and under the conditions specified the gas oil vapors are usually converted to gasoline in yields amounting to 40% to 50% based on the original feed stock.
- a catalyst preferably an acid treated clay catalyst
- the total vapors are withdrawn from chamber 8 overhead through line l0 and passed into a fractionating column l2 from which the gasoline vapors are withdrawn through a line H, thence discharged into a cooler or, condenser l6, thence withdrawn through line l'l into a receiving drum it, from which drum the normally gaseous products are withdrawn through line i9. while catalytically cracked gasoline is recovered through line 20.
- a light gas oil is withdrawn from tower i2 through line 2
- a heavier fraction is withdrawn from the bottom or column l2 through line 22 and discharged into a pump 23, thence into a furnace 24 where the fraction is heated to a temperature of from 400 F. to 950 F.
- the heated oil is withdrawn from iurnace 24 through line 25 and discharged into a thermaltreatment vessel 26 where it is permitted to remain for sufficient time to effect the desired conversion of unsaturated bodies and multi-ring --aromatic' compounds into heavy hydrocarbons.
- the heavy hydrocarbons formed as a result of the treatment in vessel 28 are withdrawn through line 28 and after pressure reduction in valve 20 are discharged into a fractionating tower or tar separator 21 where the tar is separated from the lighter gas oil portion, the heavy tar being removed through line 3
- the treatment in chamber or drum 28 is prolonged sufllciently to accomplish the desired result, and ordinarily the oil remains in the treating zone for a period of from 20 seconds to one hour or more, with best results secured by permitting the oil to remain resident in the vessel 20 for a period of about 5 minutes.
- the principal reaction taking place in vessel 26 is one in which the mono-oleflns, dioleflns, and compounds of the nature of naphthalene, anthracene, and the like are converted to tarry high molecular weight compounds which are relatively poor in hydrogen content and which may be readily separated by flashing and distillation in vessel 21 after flashing through valve 20.
- stock in line ll may be discharged into the coil 2 at some point removed from the intake thereof, since the cycle oil in line 30 usually will be at a temperature of 400'-600 F. and under those conditions it need not be discharged into the feed line I which normally would contain cold 011.
- the catalyst in chamber 0 may be in fresh feed in line I directly into furnace coil 24.
- the overhead product from chamber 21 would be fed to the coil 2.
- the overhead product in line 30 may not be returned to coil 2 but may be delivered to'another catalytic cracking zone or thermal cracking zone where it could be subjected to higher temperatures than those prevailing in chamber 8, since the stock would be relatively free of components or constituents tending to form coke.
- a process for cracking a straight run gas oil to form lower boiling hydrocarbons which comprises passing said gas oil in the absence of substantial amounts of olefin and aromatic hydrocarbons and other coke-forming constituents thru a cracking zone at a temperature above 800 F., contacting said gas oil within said crackin zone with a cracking catalyst, keeping the oil in contact with said catalyst for a period sufficient to convert a substantial portion of said oil into lower boiling hydrocarbons, separating the cracked products into a gasoline fraction, a light gas oil fraction, and a heavy gas oil fraction, coridensing the gasoline and light gas oil fractions, maintaining said heavy gas oil fraction independently of said straight run gas oil at a temperature of about 750 to 850 F. and under elevated pressure for a substantial period to polymerize coke-forming constituents contained in said heavy gas oil, thereafter separating the polymerized coke-forming constituents from said heavy gas oil fraction and recycling said heavy 5 gas oil to said catalytic cracking step.
Description
Feb. 8, 1944. c. E. HEMMINGER 2,340,960
CYCLE GAS OILS BY THERMAL TREATMENT Filed June 22, 1940 oon. ER
72A c 770 NA rm/c C04 (/M/V 25 C El V/NC DRUM CA TAL 777C com 52,3 101v CHA M3572 YM2 IZATION V5335.
7'0 WER l/EA TINC c OIL l/EA TING (:OIL
ca a yst;
Patented Feb. 8, 1944 CYCLE GAS OILS BY THERMAL TREATMENT Charles E. Hemminger, Westfield, N. .1., assignor to Standard Oil Development Company, a corporation of Delaware Application June 22, 1940, Serial No. 341,813
1 Claim.
The present invention relates to the art of treating hydrocarbons. More particularly, the present invention relates to improvements in the catalytic treatment of relatively heavy hydrocarbons such as 'a gas oil to form light fractions boiling within the gasoline range in which the cycle stock, that is to say, the unconverted hydrocarbons recovered from the catalyst zone are subjected to a thermal treatment in order to improve their cracking characteristics or properties.
It is well known that in thermal cracking of hydrocarbons the charging stock should be largely parafiinic to produce the best results. It is also known that the more a charging stock is cracked thermally, the poorer it becomes as a feed stock for further cracking. Consequently, in thermal operations there comes a time when a feed stock, due to repeated cracking, must be rejected since it becomes too refractory and too prone to form excessive coke to be further cracked. on the other hand, a feed stock for a catalytic cracking operation is preferably of a naphthenic character and should also be substantially free of aromatic compounds containing more than one benzene ring in a single condensed nucleus. If a feed stock used in a catalytic cracking operation contains compounds such as naphthalene, anthracene, phenanthrene, benzenthrene, and the like, or their alkylated derivatives, these condensed ring compounds form during the cracking operation excessive quantities of coke. Furthermore, if a feed stock in a catalytic cracking operation'contains substantial quantities of olefins, these latter compounds during the catalytic cracking operation tend to polymerize to form high molecular weight hydrocarbons which, during the catalytic conversion, are convertedto tarry r gummy deposits or cake which deposit on the catalyst and necessitata'frequent shut-downs for the purpose of removing the same to regenerate the I haveldiscovered means for conditioning the cycle stockrecovered from a catalytic operation wherein the cycle stock is improved as to its cracking properties and therefore may be recycled to the catalyst zone for further conversion without causing excessive formation of tarry deposits or coke on the catalyst.
It is an object of my invention, therefore, to condition an oil recovered from the catalytic process, which oil is not satisfactory from the standpoint of cracking characteristics, by subjecting the said oil to a mild viscosity breaking or thermal treatment operation wherein the coke-forming bodies contained in the said oil are converted to relatively heavy compounds or fractions which may be removed from the said,
My invention will be-best understood by reference to the accompanying drawing in which I represents in diagrammatic iorm an apparatus layout or flow diagram in which my perature of 825 F. The hot vapors are withdrawn through line 4 and discharged into a catalytic conversion chamber 8 where the vapors contact a catalyst, preferably an acid treated clay catalyst, and under the conditions specified the gas oil vapors are usually converted to gasoline in yields amounting to 40% to 50% based on the original feed stock. The total vapors are withdrawn from chamber 8 overhead through line l0 and passed into a fractionating column l2 from which the gasoline vapors are withdrawn through a line H, thence discharged into a cooler or, condenser l6, thence withdrawn through line l'l into a receiving drum it, from which drum the normally gaseous products are withdrawn through line i9. while catalytically cracked gasoline is recovered through line 20. A light gas oil is withdrawn from tower i2 through line 2|. This gas oil fraction may be returned to the cracking coil 2 or it may be withdrawn as a product suitable for a heating oil. Meanwhile, a heavier fraction is withdrawn from the bottom or column l2 through line 22 and discharged into a pump 23, thence into a furnace 24 where the fraction is heated to a temperature of from 400 F. to 950 F. The heated oil is withdrawn from iurnace 24 through line 25 and discharged into a thermaltreatment vessel 26 where it is permitted to remain for sufficient time to effect the desired conversion of unsaturated bodies and multi-ring --aromatic' compounds into heavy hydrocarbons. The heavy hydrocarbons formed as a result of the treatment in vessel 28 are withdrawn through line 28 and after pressure reduction in valve 20 are discharged into a fractionating tower or tar separator 21 where the tar is separated from the lighter gas oil portion, the heavy tar being removed through line 3| while the cleaned stock from which the unsaturated compounds and the multi-ring aromatic compounds have been'removed. as indicated, is withdrawn through'line 30 and returned through line I for further catament vessel 16, it may be said that good results 3 are obtained ordinarily by subjecting the oil in vessel 28 to a temperature within the range of from 400 F. to 950 F., preferably operating at about 750 F. to 850 F., and imposing a pressure of from to 300 atmospheres gauge on the oil undergoing the conditioning operation with a pressure of 30 atmospheres preferred. The treatment in chamber or drum 28 is prolonged sufllciently to accomplish the desired result, and ordinarily the oil remains in the treating zone for a period of from 20 seconds to one hour or more, with best results secured by permitting the oil to remain resident in the vessel 20 for a period of about 5 minutes. As indicated previously, the principal reaction taking place in vessel 26 is one in which the mono-oleflns, dioleflns, and compounds of the nature of naphthalene, anthracene, and the like are converted to tarry high molecular weight compounds which are relatively poor in hydrogen content and which may be readily separated by flashing and distillation in vessel 21 after flashing through valve 20.
stock in line ll may be discharged into the coil 2 at some point removed from the intake thereof, since the cycle oil in line 30 usually will be at a temperature of 400'-600 F. and under those conditions it need not be discharged into the feed line I which normally would contain cold 011. An-
L other alternative procedure is to introduce the Although the invention has been described in terms of a stationary bed type of operation, that is to say, the catalyst in chamber 0 may be in fresh feed in line I directly into furnace coil 24. In that case, and particularly where the fresh feed was a reduced crude, the overhead product from chamber 21 would be fed to the coil 2. Finally the overhead product in line 30 may not be returned to coil 2 but may be delivered to'another catalytic cracking zone or thermal cracking zone where it could be subjected to higher temperatures than those prevailing in chamber 8, since the stock would be relatively free of components or constituents tending to form coke.
It is obvious that many modifications of my invention will readily occur to those skilled in this What I claim is:
A process for cracking a straight run gas oil to form lower boiling hydrocarbons which comprises passing said gas oil in the absence of substantial amounts of olefin and aromatic hydrocarbons and other coke-forming constituents thru a cracking zone at a temperature above 800 F., contacting said gas oil within said crackin zone with a cracking catalyst, keeping the oil in contact with said catalyst for a period sufficient to convert a substantial portion of said oil into lower boiling hydrocarbons, separating the cracked products into a gasoline fraction, a light gas oil fraction, and a heavy gas oil fraction, coridensing the gasoline and light gas oil fractions, maintaining said heavy gas oil fraction independently of said straight run gas oil at a temperature of about 750 to 850 F. and under elevated pressure for a substantial period to polymerize coke-forming constituents contained in said heavy gas oil, thereafter separating the polymerized coke-forming constituents from said heavy gas oil fraction and recycling said heavy 5 gas oil to said catalytic cracking step.
CHARLES E. HEMMINGER.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US341813A US2340960A (en) | 1940-06-22 | 1940-06-22 | Cycle gas oils by thermal treatment |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US341813A US2340960A (en) | 1940-06-22 | 1940-06-22 | Cycle gas oils by thermal treatment |
Publications (1)
Publication Number | Publication Date |
---|---|
US2340960A true US2340960A (en) | 1944-02-08 |
Family
ID=23339139
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US341813A Expired - Lifetime US2340960A (en) | 1940-06-22 | 1940-06-22 | Cycle gas oils by thermal treatment |
Country Status (1)
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US (1) | US2340960A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2701231A (en) * | 1951-02-07 | 1955-02-01 | Standard Oil Dev Co | Catalytic hydrocarbon conversion starting up procedure |
US2717864A (en) * | 1951-05-26 | 1955-09-13 | Exxon Research Engineering Co | Partial hydrogenation of feed oils employed in catalytic cracking to produce motor fuels |
US2749288A (en) * | 1952-07-24 | 1956-06-05 | Universal Oil Prod Co | Method of processing hydrocarbons with a molten medium |
US2844518A (en) * | 1954-03-16 | 1958-07-22 | Exxon Research Engineering Co | Conversion of hydrocarbons |
-
1940
- 1940-06-22 US US341813A patent/US2340960A/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2701231A (en) * | 1951-02-07 | 1955-02-01 | Standard Oil Dev Co | Catalytic hydrocarbon conversion starting up procedure |
US2717864A (en) * | 1951-05-26 | 1955-09-13 | Exxon Research Engineering Co | Partial hydrogenation of feed oils employed in catalytic cracking to produce motor fuels |
US2749288A (en) * | 1952-07-24 | 1956-06-05 | Universal Oil Prod Co | Method of processing hydrocarbons with a molten medium |
US2844518A (en) * | 1954-03-16 | 1958-07-22 | Exxon Research Engineering Co | Conversion of hydrocarbons |
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