公开(公告)号：GB704781A

公开(公告)日：1954-03-03

申请号：GB525351

申请日：1951-03-05

Applicant: STANDARD OIL DEV CO

Inventor： HANSON THOMAS KENNETH ,  POTTER EDWARD BARRIE VERNON

IPC: C10G21/00

Abstract: In the solvent extraction of hydrocarbon oil fractions into relatively more paraffinic and more aromatic fractions the extract phase from one feed stock is employed as solvent for the extraction of a second fraction of overlapping or closely adjacent boiling range to the first. The second fraction is preferably the higher boiling. Conventional solvents and apparatus may be used to extract gasolene, kerosene, Diesel fuel, lubricating oils, aromatic cycle stock obtained in catalytic cracking, and fractions which have been subjected to hydrogenation, hydroforming, isomerization and the like. Light or burning fractions of increasing boiling point may be extracted using SO2 when the sulphur content of the aromatic extract increases from stage to stage while that of the raffinate decreases. Make up solvent such as SO2 or a modifying solvent may be added in the later stages. Thus, a gasoline extract is used for kerosene extraction, the kerosene extract + SO2 used for gas oil extraction, and this extract + benzol used to extract lubricating oil. Solvents recovered from the several extracts and raffinates are treated in a common recovery system. Specification 607,945 is referred to.

公开(公告)号：GB711895A

公开(公告)日：1954-07-14

申请号：GB2773752

申请日：1952-11-04

Applicant: STANDARD OIL DEV CO

Inventor： SHARP FREDERICK REGINALD PETER ,  HANSON THOMAS KENNETH

IPC: C10L1/18

Abstract: A fuel oil has admixed therewith a minor proportion of an inorganic salt of magnesium; the magnesium salt reduces the corrosion of metal parts of the furnace in which the oil is burnt. The fuel oil may be a distillate of residual fuel oil, and is one containing sulphur and/or vanadium. Suitable salts of magnesium are the sulphate, nitrate or phosphate, or a halide such as the chloride. The magnesium salt may form a slurry with the fuel oil or may be added to the fuel oil as an aqueous solution. An emulsifying agent may be added to the aqueous solution and examples of suitable emulsifying agents are given.ALSO:An iron alloy comprises 0.25 per cent. carbon, 3 per cent manganese, 17 per cent. chromium, 17 per cent. nickel, 2.5 per cent. molybdenum, 1.8 per cent. niobium and 7 per cent cobalt.

公开(公告)号：GB714584A

公开(公告)日：1954-09-01

申请号：GB410351

申请日：1951-02-20

Applicant: STANDARD OIL DEV CO

Inventor： EVANS ERIC BERTRAM ,  HANSON THOMAS KENNETH ,  POTTER EDWARD BARRIE VERNON

IPC: C10K1/26

Abstract: In a combination process for the sulphurization of organic material such as terpenes (dipentene and alpha-pinene) or the production of thiophenes as in Specification 696,439 where two molar proportions of a mono-olefin or vinyl compound react with one atomic proportion of sulphur, which sulphurizations evolve hydrogen sulphide, and for the stripping of hydrogen sulphide from a gas mixture containing it, which mixture contains a proportion of the hydrogen sulphide evolved in the sulphurization reaction, the gas mixture containing hydrogen sulphide is passed through a bed of iron oxide to deposit sulphur thereon, the spent oxide is passed to the sulphurization reactor to supply sulphur thereto, and the regenerated iron oxide is returned to the hydrogen sulphide adsorption stage. Gas streams from other sources such as oil refineries, gas works or tar distilleries may supply some of the hydrogen sulphide to be converted to sulphur. The process which preferably takes place in vapour phase may be wholly fluidized. The organic material, for example styrene, is then passed in vapour phase through a fluidized bed of sulphur supported on iron oxide, together with the catalyst which may be added separated, mixed with the feed, supported on the iron oxide or on some other support. The relatively sulphur-free oxide gravitates to the bottom and is withdrawn as a suspension in air and steam and passed to the adsorption stage. The effluent gases from the sulphurization, for example styrene, diphenyl thiophene and hydrogen sulphide, are cooled and condensed, the hydrogen sulphide passing to the adsorption stage together with sufficient air or steam to oxidize the hydrogen sulphide to sulphur, and to fluidize the iron oxide. The sulphurized oxide is removed from the top of the bed and returned to the sulphurization reactor as a suspension in nitrogen or flue gas. The catalyst for the production of thiophene may be conventional rubber vulcanization accelerators such as alkyl or aryl mercaptans, xanthates, condensation products of aromatic amines with aliphatic aldehydes, mercaptobenzathiazole or diphenylguanidine. The iron oxide, which may carry the catalyst, may itself be supported on silica gel. Superheated steam may be used to assist volatilization of high boiling point products in the sulphurization reaction and if molten sulphur impedes fluidization an inert powdered diluent such as sand or clay may be added. Specifications 554,227, 568,913; 586,914 590,456, 601,723, 623,264, and 712,618, [all in Group III] also are referred to.ALSO:In a combination process for the sulphurization of organic materials, such as fatty oils, such as lard or sperm oil, which sulphurization evolves hydrogen sulphide, and for stripping hydrogen sulphide from a gas mixture containing it, which mixture contains a proportion of the hydrogen sulphide evolved in the sulphurization reaction, the gas mixture is passed through a bed of iron oxide particles to strip the hydrogen sulphide and to deposit elemented sulphur on the oxide particles, which are then passed to the sulphurization reactor where they are contacted with the organic materials in the presence of a sulphurization catalyst thereby regenerating the iron oxide which is recycled to the hydrogen sulphide adsorption stage. The process is also applicable to the sulphurization of petroleum fractions to remove mono- and diolefinic compounds as described in Specification 712,618. Gas streams from other sources such as oil refineries, gas works or tar distilleries may supply some of the hydrogen sulphide to be converted to sulphur. The process which preferably takes place in the vapour phase, may be operated wholly on the fluidized technique. The organic materials are then passed in vapour phase through a fluidized bed of sulphur supported on iron oxide in the presence of a catalyst. The relatively sulphur-free oxide gravitates to the bottom and is removed as a light suspension in an air steam mixture and passed to the hydrogen sulphide adsorption stage. The effluent gases from the sulphurization reaction are separated and the hydrogen sulphide and inert gases therefrom are employed to fluidize the iron oxide in the adsorption stage together with sufficient air or steam to oxidize the hydrogen sulphide. The sulphurized oxide concentrates at the top of the bed, stratification being assisted by the inclusion of non-fluidized packings such as lumps of refractory, and is withdrawn as a nitrogen or flue gas suspension and returned to the reactor. The process is also applicable to the sulphurization of terpenes such as dipentene or alphapinene or to the production of thiophenes from mono-olefins or vinyl compounds as described in Specification 696,439, [Group IV (b)]. Conventional vulcanization accelerators such as alkyl or aryl mercaptans, or xanthates, condensation products of aromatic amines and aliphatic aldehydes, mercaptobenzothialyde and diphenylquanidine may be used as catalysts in the latter case. These may be introduced separately or mixed with the feed, carried on an inert support or supported on the iron oxide. Further the iron oxide may itself be supported on a silica gel support and the catalyst incorporated. Such a catalyst may be prepared by impregnating a silica hydrosol with a ferric salt, precipitating with ammonia, washing and calcining. One per cent. of mercaptobenzothiazole may then be deposited from ethanol solution. An inert powdered diluent may be added to the sulphurization reactor if the presence of molten sulphur impedes fluidization. Specifications 554,227, 568,913, 586,914, 590,456, 601,723, 623,264 also are referred to.

公开(公告)号：GB696439A

公开(公告)日：1953-09-02

申请号：GB162951

申请日：1951-01-22

Applicant: STANDARD OIL DEV CO

Inventor： HANSON THOMAS KENNETH ,  KINNARD LEONARD MATTHEW

IPC: C07D333/08

Abstract: Thiophene derivatives are produced when sulphur is reacted with an olefinic compound of the formula RCH=CH2, where R is a hydrocarbon radical or a hydrocarbon radical carrying substituents which are inert under the conditions of the reaction, the reaction being carried out in the presence of a compound which is known for use commercially as a vulcanization accelerator. Compounds mentioned for this purpose include mercaptobenzothiazole, hexamine, aldehyde amine condensation products, diphenyl guanidine, thioureas, thiophenols, dithiocarbamates, trithiocarbamates, xanthates and thiuram disulphides. The reaction is carried out by raising the temperature of the mixture of catalyst, sulphur and olefine together with a diluent if the latter is used, to a point where vigorous evolution of hydrogen sulphide occurs. Starting materials include aliphatic olefines containing up to 20 carbon atoms of which propylene, butene-1 and butene-2, the lower polymers or copolymers derived by cracking long-chain hydrocarbons such as paraffin wax. Aromatic olefins include styrene and its substitution products such as alkyl styrenes. An example is given using styrene as the olefine and mercaptobenzothiazole as the catalyst.

公开(公告)号：GB712618A

公开(公告)日：1954-07-28

申请号：GB192951

申请日：1951-01-25

Applicant: STANDARD OIL DEV CO

Inventor： WINDEBANK CHARLES SIDNEY ,  HANSON THOMAS KENNETH

IPC: C10G29/02

Abstract: Petroleum fractions are treated at elevated temperature with sulphur or a sulphur compound which liberates sulphur at the temperature used, in the presence of a nitrogen-containing rubber vulcanization accelerator. The sulphur reacts with olefins present giving a product of reduced tendency to gum. If desired, this may be separated by distillation from the complex sulphur compounds formed. Where sulphur is present as such or as disulphides, e.g. in cracked stocks, further addition of sulphur may be unnecessary. The vulcanization accelerators include nitrogen bases and their derivatives, condensation products of aldehydes with ammonia or amines, guanidines, especially aryl guanidines, and compounds containing sulphur, e.g. thioureas, dithiocarbamates, mercaptothiazoles, mercaptobenzthiazoles, and thiuram disulphides. Specific examples are zinc dimethyl (or dibutyl) dithiocarbamate, piperidine pentamethylene dithiocarbamate, and mercaptobenzthiazole. Temperature is generally 50-400, preferably 125-175 or 200-300 DEG C., using free or combined sulphur respectively. The amount of accelerator is generally up to 10 per cent. by weight of the sulphur. In an example, a reformed naphtha is refluxed with 1 per cent. of sulphur and .01 per cent. of mercaptobenzthiazole at 165 DEG C. for 7 hours. Specification 696,439, [Group IV (b)], is referred to.

公开(公告)号：GB688293A

公开(公告)日：1953-03-04

申请号：GB1530250

申请日：1950-06-19

Applicant: STANDARD OIL DEV CO

Inventor： MCLEAN DONALD HENRY ,  HANSON THOMAS KENNETH ,  HAWKINS ELEANOR RUTH

IPC: C07G99/00 ,  C10M135/04

Abstract: Sulphurized terpenes are made by reacting sulphur with a terpene or mixture of terpenes, the lower boiling components being removed from the reacted mixture by steam distillation at a temperature below the decomposition temperature of the sulphurized terpenes. They are lubricating oil additives, cf. Group III. Reaction temperatures mentioned are 135-200 DEG C., preferably 170-180 DEG C., and 1.5-2 atoms of S per mol. of terpene are used. Other amounts of S specified are 20-35 per cent, preferably 25-30 per cent, and reaction times instanced are 5-10 hours, usually 6-7 hours. Dipentene is the preferred terpene. Distillation temperatures should not substantially exceed 150 DEG C. and are preferably below 130 DEG C. e.g. 100-120 DEG C. Usually about 15-30 per cent of crude product is removed. Resins produced in the reaction are desirably removed by solvent precipitation before or after steam distillation. Petroleum ether and pentane are specified solvents. Preferably sulphurization is effected in the presence of a vulcanization accelerator, e.g. tetramethyl thiuram disulphide, mercaptobenzothiazole and diphenyl guanidine. The amount of accelerator is conveniently less than 5 per cent and preferably 1-2 per cent. In an example, dipentene and sulphur are heated at up to 175 DEG C. in the presence of a mixture of mercaptobenzothiazole and diphenyl guanidine and the product treated by (a) blowing with nitrogen to remove H2S; (b) washing with 15 per cent caustic soda; (c) steam distilled to remove 30 per cent of light ends; (d) solvent precipitated to remove 12 per cent polymer; and (e) steam distilled and precipitated as in (c) and (d), treatments (a), (b) and (d) being for comparative purposes.ALSO:A lubricating oil composition comprises a lubricating oil, preferably a mineral lubricating oil, and a minor proportion of the product of the process wherein sulphur is reacted with a terpene or mixture of terpenes and the lower boiling components are removed from the reacted mixture by steam distillation at a temperature below the decomposition temperature of the sulphurized terpenes. Usually about 15-30 per cent of crude product is removed. Resins produced in the reaction are preferably removed by solvent precipitation either before or after steam distillation. Preferably sulphurization is effected in the presence of a rubber vulcanization accelerator. For details of the process (see Group IV(b)). The additives are used in amounts of about 0.1-2 per cent, preferably about 0.3-0.5 per cent. Detergent additives may also be present, those mentioned being calcium mahogany sulphonates, calcium or barium phenates, zinc butyl or isopropyl benzoate, metal organo-phosphates and thiophosphates and preferably alkaline earth derivatives of alkyl phenol sulphides or sulphurized alkylated phenols. Detergent additives may be used in amounts of about 1 to 5 per cent, preferably about 1.5 to 2.5 per cent. In an example dipentene and sulphur are heated up to 175 DEG C for 8 1/2 hours in the presence of a mixture of mercaptobenzothiazole and diphenyl guanidine and the product treated by (a) blowing with nitrogen to remove H2S, (b) washing with 15 per cent caustic soda, (c) steam distilled to remove 30 per cent of light ends, (d) solvent precipitated to remove 12 per cent of polymer, and (e) steam disstilled and preciptated as in (c) and (d) and the products are engine tested as lubricants in admixture with a mineral oil containing 1.5 per cent of the barium salt of p-tert.-octyl phenol sulphide and 1.5 per cent of the products, it being shown that those of (c) and (e) give the best results

公开(公告)号：GB727655A

公开(公告)日：1955-04-06

申请号：GB2060951

申请日：1951-08-31

Applicant: STANDARD OIL DEV CO

Inventor： DAVIES ROY TREVOR ,  HANSON THOMAS KENNETH ,  RAE NORMAN SIDNEY

IPC: C10M169/00

Abstract: A solution of a divalent metal alkyl phenate or thiophenate in an inert solvent is reacted with elemental sulphur to give a complex reaction product as a concentrate in the inert solvent, and a proportion of a metal, ammonium or organic base salt of a petroleum mahogany acid is added to the concentrate. The final concentrate is useful as a detergent additive for lubricating oils and, as a result of the presence of the mahogany sulphonate, shows no tendency to deposit crystals on standing; in the absence of the mahogany sulphonate there is a tendency for the deposition of crystals of alkyl phenol or thiophenol, which is probably partially regenerated during the sulphurization reaction. The inert solvent may be lubricating oil and may contain a C8-C20 saturated aliphatic alcohol such as cetyl or stearyl alcohol to reduce foaming during the sulphurization reaction and to act as solubilizer of the sulphurized product. The divalent metal alkyl phenate or thiophenate may be an alkaline earth metal salt which may be a basic salt; similarly, the mahogany sulphonate may be an alkaline earth metal salt which may be a basic salt. The magnesium salts of both the alkyl phenol or thiophenol and the mahogany acid are also mentioned. The sulphurized product may be blown with carbon dioxide before or after the addition of the mahogany sulphonate. In an example, barium p-tert. octyl phenate, in mineral lubricating oil solution containing a mixture of cetyl and stearyl alcohols, is sulphurized and calcium mahogany sulphonate is then added. Specifications 586,841, 599,729 and 600,825 are referred to.