US2639304A - Purification of aromatic hydrocarbons - Google Patents
Purification of aromatic hydrocarbons Download PDFInfo
- Publication number
- US2639304A US2639304A US266107A US26610752A US2639304A US 2639304 A US2639304 A US 2639304A US 266107 A US266107 A US 266107A US 26610752 A US26610752 A US 26610752A US 2639304 A US2639304 A US 2639304A
- Authority
- US
- United States
- Prior art keywords
- hydrocarbons
- paraffin
- aromatic hydrocarbon
- mixture
- toluene
- 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims description 15
- 238000000746 purification Methods 0.000 title description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012188 paraffin wax Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- XAZKFISIRYLAEE-UHFFFAOYSA-N (+-)-trans-1,3-Dimethyl-cyclopentan Natural products CC1CCC(C)C1 XAZKFISIRYLAEE-UHFFFAOYSA-N 0.000 description 2
- QWHNJUXXYKPLQM-UHFFFAOYSA-N 1,1-dimethylcyclopentane Chemical compound CC1(C)CCCC1 QWHNJUXXYKPLQM-UHFFFAOYSA-N 0.000 description 2
- AORMDLNPRGXHHL-UHFFFAOYSA-N 3-ethylpentane Chemical compound CCC(CC)CC AORMDLNPRGXHHL-UHFFFAOYSA-N 0.000 description 2
- VLJXXKKOSFGPHI-UHFFFAOYSA-N 3-methylhexane Chemical compound CCCC(C)CC VLJXXKKOSFGPHI-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RIRARCHMRDHZAR-UHFFFAOYSA-N (+-)-trans-1,2-Dimethyl-cyclopentan Natural products CC1CCCC1C RIRARCHMRDHZAR-UHFFFAOYSA-N 0.000 description 1
- RIRARCHMRDHZAR-RNFRBKRXSA-N (1r,2r)-1,2-dimethylcyclopentane Chemical compound C[C@@H]1CCC[C@H]1C RIRARCHMRDHZAR-RNFRBKRXSA-N 0.000 description 1
- XAZKFISIRYLAEE-RNFRBKRXSA-N (1r,3r)-1,3-dimethylcyclopentane Chemical compound C[C@@H]1CC[C@@H](C)C1 XAZKFISIRYLAEE-RNFRBKRXSA-N 0.000 description 1
- 102100024482 Cell division cycle-associated protein 4 Human genes 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 101000980898 Homo sapiens Cell division cycle-associated protein 4 Proteins 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/06—Metal salts, or metal salts deposited on a carrier
- C10G29/12—Halides
-
- 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
- C07C7/14833—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds
- C07C7/1485—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds oxides; hydroxides; salts
Definitions
- An object of my invention is the provision of an improved process of hydrocarbon purification using aluminum chloride. Another object is the improvement of the efiiciency of such processes by the use of promoters. Another object is to reduce the cost of such processes. Other objects will appear in the course of the disclosure of my invention.
- One class of unwanted constituents is the paraffins, which some toluene specifications, for example, require to be held below 0.2% when the toluene is to be used in the carbons with this degree of purity without some auxiliary purifying treatment.
- paraflins as here used is a trade expression referring to nonaromatic compounds which are unsulfonatable and have boiling points close to that of the aromatic hydrocarbon.
- these parafiins have been found to be primarily naphthenic and to include the following compounds [see John R. Anderson and Carl J. Engelder, Industrial and Engineering Chemistry, vol. 3'7, pp. 541-3 (1945), and Chemical Abstracts, vol. 39. p. 3146/3 (1945)]:
- the said treatment is generally carried out by reacting the parafiins with an acid-reacting metal halide, such as aluminum chloride.
- an acid-reacting metal halide such as aluminum chloride.
- My invention consists, essentially, in reacting the hydrocarbon with aluminum chloride to which is added, as promoter, alpha picoline. Olefins and any tar formed are afterwards removed by known means.
- paraffin hydrocarbons dissolved as normally occurring impurities in a liquid aromatic hydrocarbon which is produced from coal and is from the group consisting of benzene, toluene and xylene, said paraffin hydrocarbons being unsulfonatable, non-aromatic and of such nature as to distill over with the aromatic hydrocarbon, comprising treating the said mixture with anhydrous aluminum chloride in amount between about 1% and 9% by weight of the aromatic hydrocarbon and alpha picoline in amount not less than 10% by weight of the aluminum as normally occurring impurities in liquid toluene produced from coal, said "paraflin hydrocarbons being unsulfonatable, nonaromatic and of such nature as to distill over with the toluene, comprising treating the said mixture at a temperature of about 50 C.
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)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
Patented May 19, 1953 PURIFICATION OF AROMATIC HYDRO CARBONS Frank P. Hazlett, Pittsburgh, Pa., assignor to Jones & Laughlin Steel Corporation, Pittsburgh, Pa., a corporation of Pennsylvania No Drawing. Application page 11, 1952,
Serial No. 266107 6 Claims. (Cl; 260-674) This invention is concerned with the purification of aromatic hydrocarbons, and more particularly with the reduction of the parafiin content of such hydrocarbons. This application I is a continuation in part of my application Serial No. 57,839, filed June 16,1949, and now abandoned. 7 7
An object of my invention is the provision of an improved process of hydrocarbon purification using aluminum chloride. Another object is the improvement of the efiiciency of such processes by the use of promoters. Another object is to reduce the cost of such processes. Other objects will appear in the course of the disclosure of my invention.
The common aromatic hydrocarbons benzene, toluene, and xylene, which may be recovered as by-products in the coking of coal, find considerable use as raw materials in further chemical manufacture. For these purposes it is generally required that the content of unwanted constituents be quite low. One class of unwanted constituents is the paraffins, which some toluene specifications, for example, require to be held below 0.2% when the toluene is to be used in the carbons with this degree of purity without some auxiliary purifying treatment.
The term paraflins as here used is a trade expression referring to nonaromatic compounds which are unsulfonatable and have boiling points close to that of the aromatic hydrocarbon. For example, in benzene of commercial grade produced from coal-coking operations, these parafiins" have been found to be primarily naphthenic and to include the following compounds [see John R. Anderson and Carl J. Engelder, Industrial and Engineering Chemistry, vol. 3'7, pp. 541-3 (1945), and Chemical Abstracts, vol. 39. p. 3146/3 (1945)]:
(l) Cyclohexane;
(2) Methylcyclohexane;
(3) 3-methylhexane or 3 -ethylpentane or both;
(4) Heptane or 2,2,4 trimethylpentane or both;
(5) 1,1-dimethylcyclopentane; and
(6) Trans-1,2-dimethylcyclopentane or trans- 1,3-dimethylcyclopentane or both. i
A considerable number of methods for reducing the percentage of these "paraflins have been devised, including adsorption of the parafiins on sold adsorbents, solvent extraction, azeotropic distillation, extractive distillation, and chemical reaction, particularly treatment of the parafiins to produce less undesirable lower or higher boiling point compounds. Of these various methods the last has been found to reduce the parafiin content to lowest values.
The said treatment is generally carried out by reacting the parafiins with an acid-reacting metal halide, such as aluminum chloride. Under favorable conditions,'the paraffin content of a commercially refined hydrocarbon so treated can be reduced to the 0.2% limit imposed by a number of users, provided that the temperature is kept closely below the boiling point of the aromatic hydrocarbon. Repeated treatment may be necessary in some instances to reduce the paraiiin content to the maximum limit of 0.2%; for example, if the initial paraffin content happens to be high as a result of the particular operating conditions of the coke oven which produced the aromatic hydrocarbon. I have discovered, however, a process by which reaction of the parafiins in aromatic hydrocarbons can be carried out in one stage so completely that the unreacted parafiin content lies well below the lowest limits so far set by industrial users of toluene and other aromatic hydrocarbons.
My invention consists, essentially, in reacting the hydrocarbon with aluminum chloride to which is added, as promoter, alpha picoline. Olefins and any tar formed are afterwards removed by known means. A single treatment, by the process of my invention, of toluene, for example, containing upwards of 0.50% parafiins, not only produces purified toluene containing less than 0.10% of these compounds, but does so with full speed and effectiveness at relatively reduced temperatures such as C. and 50 C. This is well below the reaction temperature of close to C. necessary for maximum effectiveness when treating toluene with aluminum chloride alone.
The following examples illustrate the operation of my invention. In these examples a sample of paraflin containing toluene stock was obtained from a batch of toluene produced as a regular by-product of coal-coking operations and of commercially refined grade, sulphuric acid washed, which is not fully purified but meets the test for nitration grade toluene in A. S. T. M. Specification D841-47 as determined by the procedure described in A. S. T. M. Specification D851-47 (see vol. 5, A. S. T. M. Stand- 5. A method of reducing the percentage of para hydrocarbons in a. mixture of a small percentage of paraffin hydrocarbons dissolved as normally occurring impurities in a liquid aromatic hydrocarbon which is produced from coal and is from the group consisting of benzene, toluene and xylene, said paraffin hydrocarbons being unsulfonatable, non-aromatic and of such nature as to distill over with the aromatic hydrocarbon, comprising treating the said mixture with anhydrous aluminum chloride in amount between about 1% and 9% by weight of the aromatic hydrocarbon and alpha picoline in amount not less than 10% by weight of the aluminum as normally occurring impurities in liquid toluene produced from coal, said "paraflin hydrocarbons being unsulfonatable, nonaromatic and of such nature as to distill over with the toluene, comprising treating the said mixture at a temperature of about 50 C. to 80 C. at about atmospheric pressure with anhydrous aluminum chloride in amount about 3% by weight and alpha picoline in amount about 20% by weight of the anhydrous aluminum chloride, and agitating the mixture, until the content of "paraifin hydrocarbons is reduced to about 0.1% or less by volume in a single treatment.
FRANK P. HAZLETT.
Name Date Ipatiefi et a1. Aug. 3, 1937 Hepp et a1 Jan. 11, 1949 Number
Claims (1)
1. A METHOD OF REDUCING THE PERCENTAGE OF "PARAFFIN " HYDROCARBONS IN A MIXTURE OF A SMALL PERCENTAGE OF "PARAFFIN" HYDROCARBONS DISSOLVED AS NORMALLY OCCURING IMPURITIES IN A LIQUID AROMATIC HYDROCARBON PRODUCED FROM COAL, SAID "PARAFFIN" HYDROCARBONS BEING UNSULFONATABLE, NONAROMATIC AND OF SUCH NATURE AS A DISTILL OVER WITH THE AROMATIC HYDROCARBON, COMPRISING TREATING THE SAID MIXTURE WITH ANHYDROUS ALUMINUM CHLORIDE AND ALPHA PICOLINE, AT A TEMPERATURE AND PRESSURE BELOW THE BOILING POINT OF THE AROMATIC HYDROCARBON, UNTIL THE PERCENTAGE OF SAID "PARAFFIN" HYDROCARBONS IN THE MIXTURE IS REDUCED TO ABOUT 0.2% OR LESS BY VOLUME.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US266107A US2639304A (en) | 1952-01-11 | 1952-01-11 | Purification of aromatic hydrocarbons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US266107A US2639304A (en) | 1952-01-11 | 1952-01-11 | Purification of aromatic hydrocarbons |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2639304A true US2639304A (en) | 1953-05-19 |
Family
ID=23013202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US266107A Expired - Lifetime US2639304A (en) | 1952-01-11 | 1952-01-11 | Purification of aromatic hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2639304A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2935470A (en) * | 1955-03-11 | 1960-05-03 | Standard Oil Co | Extraction process for recovery of aromatic hydrocarbons utilizing pyridine-bf3 or picoline-bf3 as the solvent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2088598A (en) * | 1935-03-07 | 1937-08-03 | Universal Oil Prod Co | Manufacture of alkylated cyclic hydrocarbons |
| US2458777A (en) * | 1945-12-17 | 1949-01-11 | Phillips Petroleum Co | Purification of hydrocarbons |
-
1952
- 1952-01-11 US US266107A patent/US2639304A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2088598A (en) * | 1935-03-07 | 1937-08-03 | Universal Oil Prod Co | Manufacture of alkylated cyclic hydrocarbons |
| US2458777A (en) * | 1945-12-17 | 1949-01-11 | Phillips Petroleum Co | Purification of hydrocarbons |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2935470A (en) * | 1955-03-11 | 1960-05-03 | Standard Oil Co | Extraction process for recovery of aromatic hydrocarbons utilizing pyridine-bf3 or picoline-bf3 as the solvent |
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