GB650571A - Hydrocarbon complexes - Google Patents
Hydrocarbon complexesInfo
- Publication number
- GB650571A GB650571A GB4818/48A GB481848A GB650571A GB 650571 A GB650571 A GB 650571A GB 4818/48 A GB4818/48 A GB 4818/48A GB 481848 A GB481848 A GB 481848A GB 650571 A GB650571 A GB 650571A
- Authority
- GB
- United Kingdom
- Prior art keywords
- thiourea
- complexes
- hydrocarbons
- hydrocarbon
- complex
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/08—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring
- C07C13/10—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring with a cyclopentane ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/16—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring
- C07C13/18—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring with a cyclohexane ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/152—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by forming adducts or complexes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C9/00—Aliphatic saturated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C9/00—Aliphatic saturated hydrocarbons
- C07C9/14—Aliphatic saturated hydrocarbons with five to fifteen carbon atoms
- C07C9/16—Branched-chain hydrocarbons
-
- 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
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
Thiourea or a solution thereof is contacted with an aliphatic branched chain hydrocarbon, a cyclo-aliphatic hydrocarbon or a hydrocarbon containing a cyclo-aliphatic or branched chain aliphatic radical with at least 5 carbon atoms to form crystalline complexes. Isoparaffins, naphthenes, iso-olefins, cyclo-olefins or alkaryl hydrocarbons having at least one isoparaffin radical of 5 or more carbon atoms form complexes when used alone or in admixture with other materials. Separation, concentration, and purification of hydrocarbons may be effected. Complexes formed at about room temperature contain about 3-4 parts by weight of thiourea for each part of hydrocarbon. If heated above 50 DEG C. before crystallizing, the ratio is usually about 1 : 1. When a solvent such as water or alcohol is present, solvent of crystallization may be present in the complex. Non-crystalline complexes are formed at elevated temperatures or with larger amounts of solvents. Numerous isoparaffins, naphthenes, including polycyclic naphthenes, iso-olefins, including di-iso-olefins, and cyclo-olefins, including terpenes, which form complexes, are specified. They may be mixed with thiourea in the presence of solvents or diluents for the hydrocarbons, especially other hydrocarbons such as normal paraffins and aromatics, which may be present as an impurity, as in cracked gasoline. Thiourea solvents may also be present and by choice of these, selected fractions or groups of hydrocarbons only permitted to form complexes. Such solvents are water, lower alcohols and glycols, and expecially water-methanol mixtures. Complex formation may be effected in stages, if desired with varying thiourea solution concentrations to yield different complexes. By varying the temperature, desirable fractions only can be permitted to crystallize as complexes, other complexes remaining in solution. Fractional crystallization of complexes is therefore used to separate hydrocarbon fractions. Contact of reactants may be by concurrent or counter-current fluid processes, moving or fixed bed, slurry, emulsion or solvent extraction processes. Separation of complex is effected by decantation, settling, filtration or centrifuging. It may then be washed prior to decomposition by heating or solvent extraction. By heating to about 150 DEG F., stratification into a hydrocarbon and a thiourea layer occurs. By distillation, if desired with inert gas or steam, separation of the liberated hydrocarbons into fractions is possible. Solvents for thiourea, such as water, alcohols or glycols, or for hydrocarbons, such as ether, may be added with mild heating when stratification occurs. By treating a hydrocarbon mixture with, for example, alcoholic ethanolamine or acetamide at the same time, prior to or after the thiourea treatment aromatics and normal paraffins may also be separated. Similar separations may be made by combining with a urea treatment which gives complexes of normal hydrocarbons. Where large amounts of a complex are to be formed, a temperature above 75 DEG C. may be used in treating with aqueous thiourea, when a hydrocarbon layer containing most of the complex is formed, said complex having a minimum thiourea: hydrocarbon ratio. Similar complexes of low ratio are formed at about 50-75 DEG C. using a minor proportion of water or alcohol. Crystallization in stages may be effected by step-wise addition of thiourea, if desired using solutions of different concentrations, or by control or temperature. The process is applicable to treatment of the feed or recycled feed of an isomerization process to remove iso hydrocarbons of an alkylate product to remove alkylate with or without isoparaffin, to the production of fuels by removal of isoparaffins or naphthenes from gasolines for blending purposes or for hydroforming, and to the separation of specific naphthenes or triptane. The complexes may be modified as by treatment with hydrochloric acid or acetic anhydride to give the hydrochloride or acetate salts. The complexes are useful for insecticides and fumigants, and for storage of volatile hydrocarbons. Examples are given of the treatment with saturated methanol solution of thiourea at 22 DEG C., and with a 50 per cent solution of thiourea in methyl or ethyl alcohol at 10-17 DEG C. of various hydrocarbons and hydrocarbon mixtures including a straight run petroleum fraction, with complex formation and, in some cases, recovery of hydrocarbons.ALSO:Thiourea or a solution thereof is contacted with an hydrocarbon oil containing aliphatic branched chain hydrocarbons, cyclo-aliphatic hydrocarbons or hydrocarbons containing a cyclo-aliphatic or branched chain aliphatic radical with at least 5 carbon atoms to form crystalline complexes. Isoparaffins, naphthenes, iso-olefins, cyclo-olefins or alkaryl hydrocarbons having at least one isoparaffin radical of 5 or more carbon atoms, form complexes whereby separation, concentration, and purification of hydrocarbons may be effected. Complexes formed at about room temperature contain about 3-4 parts by weight of thiourea for each part of hydrocarbon. If heated above 50 DEG C. before crystallizing, the ratio is usually about 1 : 1. When a solvent such as water or alcohol is present, solvent of crystallization may be present in the complex. Non-crystalline complexes are formed at elevated temperatures or with larger amounts of solvents. Mixing with thiourea may be effected in the presence of solvents or diluents for the hydrocarbons, especially other hydrocarbons such as normal paraffins and aromatics, which may be present as an impurity, as in cracked gasoline. Thiourea solvents may also be present and by choice of these, selected fractions or groups of hydrocarbons only permitted to form complexes. Such solvents are water, lower alcohols and glycols, and especially water-methanol mixtures. Complex formation may be effected in stages, if desired with varying thiourea solution concentrations to yield different complexes. By varying the temperature, desirable fractions only can be permitted to crystallize as complexes, other complexes remaining in solution. Fractional crystallization of complexes is, therefore, used to separate hydrocarbon fractions. Contact of reactants may be by concurrent or countercurrent fluid processes, moving or fixed bed, slurry, emulsion or solvent extraction processes. Separation of complex is effected by decantation, settling, filtration or centrifuging. It may then be washed prior to decomposition by heating or solvent extraction. By heating to about 150 DEG F., stratification into a hydrocarbon and a thiourea layer occurs. By distillation, if desired with inert gas or steam, separation of the liberated hydrocarbons into fractions is possible. Solvents for thiourea, such as water, alcohols or glycols, or for hydrocarbons, such as ether, may be added with mild heating when stratification occurs. By treating a hydrocarbon mixture with, for example, alcoholic ethanolamine or acetamide at the same time, prior to or after the thiourea treatment, aromatics and normal paraffins may also be separated. Similar separations may be made by combining with a urea treatment which gives complexes of normal hydrocarbons. Where large amounts of a complex are to be formed, a temperature above 75 DEG C. may be used in treating with aqueous thiourea, when a hydrocarbon layer containing most of the complex is formed, said complex having a minimum thiourea: hydrocarbon ratio. Similar complexes of low ratio are formed at about 50-75 DEG C. using a minor proportion of water or alcohol. Crystallization in stages may be effected by step-wise addition of thiourea, if desired using solutions of different concentrations, or by control of temperature. The process is applicable to the production of fuels by removal of isoparaffins or naphthenes from gasolines for blending purposes or for hydroforming, and to the separation of specific naphthenes or triptane. The complexes may be modified as by treatment with hydrochloric acid or acetic anhydride to give the hydrochloride or acetate salts. Examples are given of the treatment with a saturated methanol solution of thiourea at 22 DEG C. and with a 50 per cent solution of thiourea in methyl or ethyl alcohol at 10-17 DEG C. of various hydrocarbons and hydrocarbon mixtures including a straight-run petroleum fraction.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US73018247 US2499820A (en) | 1947-02-21 | 1947-02-21 | Thiourea-hydrocarbon complexes |
Publications (1)
Publication Number | Publication Date |
---|---|
GB650571A true GB650571A (en) | 1951-02-28 |
Family
ID=32736647
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB4818/48A Expired GB650571A (en) | 1947-02-21 | 1948-02-18 | Hydrocarbon complexes |
Country Status (5)
Country | Link |
---|---|
US (1) | US2499820A (en) |
DE (1) | DE893945C (en) |
FR (1) | FR961883A (en) |
GB (1) | GB650571A (en) |
NL (1) | NL72927C (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109096034A (en) * | 2018-07-17 | 2018-12-28 | 天津大学 | The new process and device of coupling reaction and separation separation normal hydrocarbon and isohydrocarbon |
Families Citing this family (75)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2676167A (en) * | 1954-04-20 | Separation process | ||
US2689845A (en) * | 1954-09-21 | Sepakating organic compounds | ||
US2695283A (en) * | 1954-11-23 | Method of forming urea and tfflourea | ||
US2732413A (en) * | 1956-01-24 | Process for the recovery of benzene by | ||
US2804451A (en) * | 1957-08-27 | Urea adducts of organic sulfur | ||
US2759918A (en) * | 1956-08-21 | Gorin | ||
US2719145A (en) * | 1955-09-27 | Process for effecting complex | ||
US2642422A (en) * | 1953-06-16 | Gorin | ||
US2653122A (en) * | 1953-09-22 | Fractional separation of oil with a complexing agent | ||
US2642424A (en) * | 1953-06-16 | Method of separating hydrocarbons | ||
US2676141A (en) * | 1954-04-20 | Process fok | ||
US2653123A (en) * | 1953-09-22 | Continuous process for separation | ||
US2642423A (en) * | 1953-06-16 | Charge | ||
US2666048A (en) * | 1954-01-12 | Separation of low molecular weight | ||
US2658060A (en) * | 1953-11-03 | Process for centrifugal separation | ||
US2698321A (en) * | 1954-12-28 | Flash | ||
US2731456A (en) * | 1956-01-17 | Sub-zone | ||
US2731455A (en) * | 1956-01-17 | Pour point reduction of petroleum oil | ||
US2774752A (en) * | 1956-12-18 | Process for treating hydrocarbons with thiourea | ||
US2685578A (en) * | 1954-08-03 | Hydrocarbon separation process | ||
US2759915A (en) * | 1956-08-21 | Gorin | ||
US2681302A (en) * | 1954-06-15 | Separ | ||
US2681334A (en) * | 1954-06-15 | Formation of urea complexes with | ||
US2653147A (en) * | 1953-09-22 | Separation process | ||
US2681303A (en) * | 1954-06-15 | separation of hydrocarbons and hydrocarbon | ||
US2632002A (en) * | 1953-03-17 | Countercurkent sltjbb | ||
US2672457A (en) * | 1954-03-16 | Pbocess for the decomposition of | ||
US2640051A (en) * | 1953-05-26 | Process for the decomposition of | ||
US2735843A (en) * | 1956-02-21 | weedman | ||
US2739144A (en) * | 1956-03-20 | Iio hsvm | ||
US2681335A (en) * | 1954-06-15 | Gorin | ||
US2716113A (en) * | 1955-08-23 | Separation process | ||
US2759917A (en) * | 1956-08-21 | Recovery of cyclohexane and methyl | ||
US2663703A (en) * | 1953-12-22 | Purification of stkaight-chain | ||
US2663671A (en) * | 1953-12-22 | Method of breaking a urea complex | ||
US2569985A (en) * | 1948-02-16 | 1951-10-02 | Shell Dev | Thiourea-ketone complexes |
US2594481A (en) * | 1948-09-30 | 1952-04-29 | Standard Oil Co | Separation of alcohols |
US2637681A (en) * | 1948-12-09 | 1953-05-05 | Texas Co | Fractional separation of wax from a hydrocarbon mixture using an organic complexing agent and a solvent |
US2606140A (en) * | 1948-12-30 | 1952-08-05 | Texas Co | Separation of wax constituents and the like from oil |
US2635986A (en) * | 1949-02-10 | 1953-04-21 | Texas Co | Continuous process for separation of waxlike constituents from oil |
US2604430A (en) * | 1949-02-24 | 1952-07-22 | Texas Co | Continuous process for separation of waxlike constituents from oil |
US2661317A (en) * | 1949-03-17 | 1953-12-01 | Texas Co | Separation of wax constituents and the like from oil |
US2666020A (en) * | 1949-06-07 | 1954-01-12 | Sepaeation of wax-like constituents | |
US2642378A (en) * | 1949-09-13 | 1953-06-16 | Socony Vacuum Oil Co Inc | Separation of wax from residual lubricating oil |
US2642379A (en) * | 1949-09-13 | 1953-06-16 | Socony Vacuum Oil Co Inc | Separation of wax and asphalt from hydrocarbon oil |
US2599130A (en) * | 1949-09-19 | 1952-06-03 | Marathon Corp | Laminated sheet material |
US2577202A (en) * | 1949-09-30 | 1951-12-04 | Process for separating organic | |
US2606214A (en) * | 1949-09-30 | 1952-08-05 | Standard Oil Co | Method of removing inhibitors for urea adduct formation |
US2773858A (en) * | 1950-03-27 | 1956-12-11 | Manuel H Gorin | Method of preparing expanded urea |
US2758108A (en) * | 1950-04-10 | 1956-08-07 | Phillips Petroleum Co | Preparation of adduct of urea or thiourea in the presence of an aqueous solution of monoethylamine |
US2723220A (en) * | 1950-04-10 | 1955-11-08 | Phillips Petroleum Co | Dewaxing of lubricating oil |
GB714327A (en) * | 1950-05-17 | 1954-08-25 | Anglo Iranian Oil Co Ltd | Improvements in or relating to the production of urea in finely divided form and to the refining of petroleum by means of urea in finely divided form |
DE859891C (en) * | 1950-07-08 | 1952-12-18 | Basf Ag | Process for the decomposition of mixtures of organic substances |
DE856296C (en) * | 1950-07-08 | 1952-11-20 | Basf Ag | Process for the decomposition of mixtures of organic substances |
US2618664A (en) * | 1950-07-29 | 1952-11-18 | Texas Co | Process for isolating phenolic compounds from mixtures thereof |
US2618665A (en) * | 1950-07-29 | 1952-11-18 | Texas Co | Process for isolating phenolic compounds from mixtures thereof |
US2744887A (en) * | 1950-08-03 | 1956-05-08 | Phillips Petroleum Co | Decomposing urea adducts by countercurrently contacting the urea adduct with a hot gas, removing the urea fines and recycling the larger urea particles |
US2766269A (en) * | 1950-10-24 | 1956-10-09 | British Petroleum Co | Production of esters |
US2700664A (en) * | 1950-11-17 | 1955-01-25 | Phillips Petroleum Co | Separation of organic compounds by adduct formation |
FR1057344A (en) * | 1952-05-24 | 1954-03-08 | ||
GB737235A (en) * | 1952-09-17 | 1955-09-21 | Metallgesellschaft Ag | Method of carrying out polymerisation reactions |
US2798102A (en) * | 1952-10-25 | 1957-07-02 | Union Oil Co | Method of decomposing werner complex clathrates |
BE524716A (en) * | 1952-12-31 | 1900-01-01 | ||
US2779710A (en) * | 1953-07-01 | 1957-01-29 | Sonneborn Sons Inc L | Process of upgrading petrolatum |
US2799623A (en) * | 1953-07-16 | 1957-07-16 | Ashland Oil Inc | Process for separating waxes from oil |
US2801993A (en) * | 1953-08-11 | 1957-08-06 | Rosenstein Ludwig | Expanded thiourea |
NL98702C (en) * | 1953-09-23 | 1961-08-15 | ||
US2849513A (en) * | 1953-12-07 | 1958-08-26 | Union Oil Co | Separation of hydrocarbons by clathrate formation with werner complex compounds |
FR1104947A (en) * | 1954-05-19 | 1955-11-25 | ||
AT195003B (en) * | 1954-09-18 | 1958-01-25 | Edeleanu Gmbh | Process and device for separating the paraffins which form adducts with urea or thiourea from hydrocarbon oils |
DE957328C (en) * | 1954-11-27 | 1957-01-31 | Edeleanu Gmbh | Process for the continuous separation of paraffins from hydrocarbon oils by adduct formation |
DE1049032B (en) * | 1955-04-29 | 1959-01-22 | Oelwerke Julius Schindler G M | Process for the continuous dewaxing of hydrocarbon oils using urea adducts |
US2906744A (en) * | 1956-03-15 | 1959-09-29 | Standard Oil Co | Insecticidal compositions |
DE1030491B (en) * | 1956-03-31 | 1958-05-22 | Scholven Chemie Ag | Process for the separation of mixtures of substances by means of urea using a diluent |
US3132084A (en) * | 1960-09-23 | 1964-05-05 | Texaco Inc | Complex forming dewaxing composition and process |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2221301A (en) * | 1939-02-13 | 1940-11-12 | Herman B Kipper | Treatment of unsaturated hydrocarbon oils |
-
0
- FR FR961883D patent/FR961883A/fr not_active Expired
-
1947
- 1947-02-21 US US73018247 patent/US2499820A/en not_active Expired - Lifetime
-
1948
- 1948-02-18 GB GB4818/48A patent/GB650571A/en not_active Expired
- 1948-02-18 NL NL138905A patent/NL72927C/xx active
- 1948-10-02 DE DEP14707D patent/DE893945C/en not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109096034A (en) * | 2018-07-17 | 2018-12-28 | 天津大学 | The new process and device of coupling reaction and separation separation normal hydrocarbon and isohydrocarbon |
CN109096034B (en) * | 2018-07-17 | 2021-09-03 | 天津大学 | Process and device for separating normal hydrocarbon and isomeric hydrocarbon by reaction separation coupling |
Also Published As
Publication number | Publication date |
---|---|
FR961883A (en) | 1950-05-24 |
NL72927C (en) | 1953-08-15 |
US2499820A (en) | 1950-03-07 |
DE893945C (en) | 1953-10-22 |
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