US2616835A - Process for removing mercaptans from mineral oils - Google Patents
Process for removing mercaptans from mineral oils Download PDFInfo
- Publication number
- US2616835A US2616835A US179812A US17981250A US2616835A US 2616835 A US2616835 A US 2616835A US 179812 A US179812 A US 179812A US 17981250 A US17981250 A US 17981250A US 2616835 A US2616835 A US 2616835A
- Authority
- US
- United States
- Prior art keywords
- fraction
- caustic
- boiling
- naphtha
- mineral oils
- 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
- 238000000034 method Methods 0.000 title claims description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title description 6
- 239000002480 mineral oil Substances 0.000 title description 3
- 239000003518 caustics Substances 0.000 claims description 20
- 238000009835 boiling Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- -1 aromatic mercaptans Chemical class 0.000 description 4
- 238000004523 catalytic cracking Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 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
- C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
Definitions
- the present invention is concerned with the refining of mineral oils and is more particularly concerned with the removal of mercaptan compounds from naphthas from catalytic cracking.
- Naphthas obtained by the catalytic cracking of hydrocarbons contain unstable aromatic mercaptans and dioleflns which react to form undesirable gums and resins when the naphtha is exposed to air or prolonged heating.
- the washed naphtha is then injected into the overhead condenser inlet line and re ⁇ mixed with the light naphtha and gas fractions.
- the low pressure gas volume is held to a minimum and is unchanged'from normal operating procedures.
- the total effluent from a catalytic cracking reaction zone is introduced by line l to the lower part of fractionating zone 2 when it is subjected to the usual distillation and fractionating processing to give a light overhead, and naphtha and gas oil side cuts.
- the liquid and gas from condenser 4 are passed to separator 5 from which low pressure gas is removed through line 6 and low pressure distillate through line 1.
- a further feature of the invention involves the removal of a rough fraction boiling from about 250 F. up to abouti/00 F.7through line 8. This fraction is cooled in cooler 9 and a portion thereof may be returned as reflux through line I0.
- the remainder of this fraction is passed to contacting zone Il where it is passed countercurrent to a caustic soda solution of 5% to 20% strength introduced through line [3 at a temperature between and 150 F.
- a treat of 1-'5% of caustic by volume on naphtha usually suffices for removing the aromatic mercaptans.
- the caustic removes the troublesome aromatic mercaptans from the roughly fractionated naphtha. Since most of the gas and acidic components have been removed from this fraction the caustic requirements are materially lowered.
- the washed naphtha is then passed by line l2 to condenser 4 where it ismixed with the overhead condensate.
- the heavy naphtha is recombined with the gas and acts to dissolve large portions of it in the low pressure distillate thus avoiding overloading the low pressure compressors in subsequent processing.
- the spent caustic is removed from contactor I l through line I4 and passed to the sewer or to mercaptan recovery units.
- Process for treating a catalytically cracked mixture of hydrocarbons boiling in the naphtha range which comprises fractionally distilling said mixture to form an overhead vapor fraction boiling up to about 250 F., removing a second fraction boiling in the range of about 250 F. to 400 F., caustic washing said second fraction, combining the overhead vapor and the caustic washed fraction, thereafter condensing at least a portion of the said vapor fraction while in admixture and contact with the said caustic washed fraction.
- Process for removing mercaptans from the products of a catalytic cracking operation which comprises fractionally distilling said products in a distillation column to form various boiling range fractions; removing. a rst fraction boilingup to about 250 overhead as a vapor, removing a second fraction boiling roughly between 250 F.
- Process as in claim 4 intwhich a part of the' cooled side stream is returned to the distillation column as reux.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
W( H. RUPP Nov. 4, '1952 PROCESS FOR REMOVING MERCAPTANS FROM MINERAL ,OILS
Filed Aug. 16. 195o U :.m DSU .E/ mam i doku/ZOU I |20 m4mm wl/ll# Patented Nov. 4, 1952 i PROCESS FOR REMOVING MERCPTAN S FROM MINERAL OILS Walter. H. Rupp, Mountainside, N. VJ assigner to `Standard Oil Development Company, a corporation of Delaware Application August 16, 1950, Serial No. 179,812
6 Claims. 1
The present invention is concerned with the refining of mineral oils and is more particularly concerned with the removal of mercaptan compounds from naphthas from catalytic cracking.
Naphthas obtained by the catalytic cracking of hydrocarbons contain unstable aromatic mercaptans and dioleflns which react to form undesirable gums and resins when the naphtha is exposed to air or prolonged heating.
It is known to remove these mercaptans by treatment with caustic soda. However, the naphtha fractions so treated often contain considerable quantities of hydrogen sulfide and carbon dioxide with the result that caustic consumption is excessive. In order to avoid excessive caustic consumption it has been proposed to separate a well fractionated light side stream from the catalytic naphtha, strip it to specification boiling point and wash this cut with caustic. This process, however, has the disadvantage that the absence of the heavy naphtha increases gas production by reducing the mols of liquid in equilibrium with the gases vented from the top of the boiling between about 250v and about 400 F. containing 1-5% of the hydrogen sulfide. The rough cut vnaphtha contains the aromatic mercaptans boiling about 300 F. and higher. This is cooled and washed with .01 to 0.2 volume of caustic per, volume of rough cut naphtha, preferably in a' countercurrent contacter, at 80-150 F. The contactor is of conventional type having either perforated plates, packing or other contacting devices. The washed naphtha is then injected into the overhead condenser inlet line and re` mixed with the light naphtha and gas fractions.
By so doing, the low pressure gas volume is held to a minimum and is unchanged'from normal operating procedures.
For a further understanding of the invention,
reference may be had to the accompanying drawing in which the single figure is an elevational view, generally diagrammatic, showing an apparatus embodying the improvement of the presenty invention.
Referring now to this drawing, the total effluent from a catalytic cracking reaction zone is introduced by line l to the lower part of fractionating zone 2 when it is subjected to the usual distillation and fractionating processing to give a light overhead, and naphtha and gas oil side cuts.
According to the present invention, all fractions boiling below 250 F. and taken overhead through line 3, and condensed in condenser 4. The liquid and gas from condenser 4 are passed to separator 5 from which low pressure gas is removed through line 6 and low pressure distillate through line 1. A further feature of the invention involves the removal of a rough fraction boiling from about 250 F. up to abouti/00 F.7through line 8. This fraction is cooled in cooler 9 and a portion thereof may be returned as reflux through line I0. The remainder of this fraction is passed to contacting zone Il where it is passed countercurrent to a caustic soda solution of 5% to 20% strength introduced through line [3 at a temperature between and 150 F. A treat of 1-'5% of caustic by volume on naphtha usually suffices for removing the aromatic mercaptans. In this operation the caustic removes the troublesome aromatic mercaptans from the roughly fractionated naphtha. Since most of the gas and acidic components have been removed from this fraction the caustic requirements are materially lowered. The washed naphtha is then passed by line l2 to condenser 4 where it ismixed with the overhead condensate. By operating in this manner the heavy naphtha is recombined with the gas and acts to dissolve large portions of it in the low pressure distillate thus avoiding overloading the low pressure compressors in subsequent processing. The spent caustic is removed from contactor I l through line I4 and passed to the sewer or to mercaptan recovery units.
The nature and objects of the present invention having been thus described and illustrated, what is claimedA as new and useful and is desired to be secured by Letters Patent is:
1. Process for treating a catalytically cracked mixture of hydrocarbons boiling in the naphtha range which comprises fractionally distilling said mixture to form an overhead vapor fraction boiling up to about 250 F., removing a second fraction boiling in the range of about 250 F. to 400 F., caustic washing said second fraction, combining the overhead vapor and the caustic washed fraction, thereafter condensing at least a portion of the said vapor fraction while in admixture and contact with the said caustic washed fraction.
2. Process as described in claim 1 in which the side stream fraction is caustic washed with between .01 and 0.2 volume of caustic per volume of side stream.
3. Process as described in claim 1 in which the y 3 side stream is caustic treated at a temperature between about 80 F. and 150 F.
4. Process for removing mercaptans from the products of a catalytic cracking operation which comprises fractionally distilling said products in a distillation column to form various boiling range fractions; removing. a rst fraction boilingup to about 250 overhead as a vapor, removing a second fraction boiling roughly between 250 F.
combining the overhead vapor and the caustic washed fraction, thereafter condensing at least a portion of the said vapor fraction While in ad mixture and contact with the said caustic washed fraction.
5. Process as in claim 4 intwhich a part of the' cooled side stream is returned to the distillation column as reux.
4 6. Process as in claim 4 in which the cooled side stream is caustic washed with between .01 and 0.2 volume of caustic per volume of side stream at a temperature between 80 F. and 150 F.
WALTER H. RUPP.
REFERENCES CITED.
The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,827,537 Morrell Oct. 13, 1931 2,070,295 Morrell Feb. 9, 1937 2,090,007 MacKenzie Aug. 17, 1937 2,297,537 Craig et al. Sept. 29, 1942 2,343,927 Hellman July 20, 1943
Claims (1)
1. PROCESS FOR TREATING A CATALYTICALLY CRACKED MIXTURE OF HYDROCARBONS BOILING IN THE NAPHTHA RANGE WHICH COMPRISES FRACTIONALLY DISTILLING SAID MIXTURE TO FORM AN OVERHEAD VAPOR FRACTION BOILING UP TO ABOUT 250* F., REMOVING A SECOND FRACTION BOILING IN THE RANGE OF ABOUT 250* F. TO 400* F., CAUSTIC WASHING SAID SECOND FRACTION, COMBINING THE OVERHEAD VAPOR AND THE CAUSTIC WASHED FRACTION, THEREAFTER CONDENSING AT LEAST A PORITON OF
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US179812A US2616835A (en) | 1950-08-16 | 1950-08-16 | Process for removing mercaptans from mineral oils |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US179812A US2616835A (en) | 1950-08-16 | 1950-08-16 | Process for removing mercaptans from mineral oils |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2616835A true US2616835A (en) | 1952-11-04 |
Family
ID=22658091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US179812A Expired - Lifetime US2616835A (en) | 1950-08-16 | 1950-08-16 | Process for removing mercaptans from mineral oils |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2616835A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1283424B (en) * | 1959-09-08 | 1968-11-21 | Shell Int Research | Process for the production of a light, copper non-corrosive hydrocarbon oil |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1827537A (en) * | 1926-06-28 | 1931-10-13 | Universal Oil Prod Co | Desulphurization and purification of hydrocarbon oil |
| US2070295A (en) * | 1933-09-15 | 1937-02-09 | Universal Oil Prod Co | Treatment of hydrocarbon oils |
| US2090007A (en) * | 1928-09-26 | 1937-08-17 | Texas Co | Manufacture of motor fuel |
| US2297537A (en) * | 1940-02-17 | 1942-09-29 | Richfield Oil Corp | Petroleum refining |
| US2343927A (en) * | 1940-03-11 | 1944-03-14 | Atlantic Refining Co | Conversion of hydrocarbon oils |
-
1950
- 1950-08-16 US US179812A patent/US2616835A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1827537A (en) * | 1926-06-28 | 1931-10-13 | Universal Oil Prod Co | Desulphurization and purification of hydrocarbon oil |
| US2090007A (en) * | 1928-09-26 | 1937-08-17 | Texas Co | Manufacture of motor fuel |
| US2070295A (en) * | 1933-09-15 | 1937-02-09 | Universal Oil Prod Co | Treatment of hydrocarbon oils |
| US2297537A (en) * | 1940-02-17 | 1942-09-29 | Richfield Oil Corp | Petroleum refining |
| US2343927A (en) * | 1940-03-11 | 1944-03-14 | Atlantic Refining Co | Conversion of hydrocarbon oils |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1283424B (en) * | 1959-09-08 | 1968-11-21 | Shell Int Research | Process for the production of a light, copper non-corrosive hydrocarbon oil |
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