US3761532A - Ortho dialkyl benzene preparation via dehydrocyclization process - Google Patents

Ortho dialkyl benzene preparation via dehydrocyclization process Download PDF

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Publication number
US3761532A
US3761532A US00022337A US3761532DA US3761532A US 3761532 A US3761532 A US 3761532A US 00022337 A US00022337 A US 00022337A US 3761532D A US3761532D A US 3761532DA US 3761532 A US3761532 A US 3761532A
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United States
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percent
orthodialkyl
detergent
hexadecane
grams
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Expired - Lifetime
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US00022337A
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English (en)
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Gramont A De
J Maurin
J Weisang
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Compagnie Francaise de Raffinage SA
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Compagnie Francaise de Raffinage SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
    • C07C5/41—Catalytic processes
    • C07C5/412—Catalytic processes with metal oxides or metal sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
    • C07C5/41—Catalytic processes
    • C07C5/415—Catalytic processes with metals
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds

Definitions

  • ABSTRACT Salts of orthodialkyl benzene sulfonates have been disclosed as having excellent detersive and biode-gradability properties.
  • a process for manufacturing these compounds has also been disclosed. In this process, paraffinic stock of certain carbon atom range is reacted with the aid ofa dehydrocyclization catalyst to produce the dialkyl benzene precursors.
  • compositions having biodegradable detergent properties More particularly this invention pertains to compositions consisting primarily of orthodialkylbenzene sulfonates having straight saturated hydrocarbon chains; further, the invention also relates to an economical process of obtaining these compositions.
  • alkyl sulfates which are of limited use due to their liquid state
  • alkyl sulfonates and alkyl benzene sulfonates which are in solid form and are of much wider use.
  • the largest number of detergents is represented at the present time by the alkyl benzene sulfonates which are prepared by alkylation of aromatic hydrocarbons, primarily benzene, by chlorinated paraffins or olefins.
  • the industry is therefore tending to produce more and more straight-chain alkyl benzene sulfates without any tertiary carbon, but isomerization of the alkyl radical is difficult to avoid.
  • the present invention solves the problem of the production of straight-chain alkyl benzene sulfonates and makes it possible to produce them under economic conditions, i.e., substantially only the normal or straight-chain dialkyl benzenes are obtained.
  • One object ofthe present invention is to provide iridustry with new detergents which can be preparedby an economical process.
  • Another object of the invention is to provide new biodegradable detergents.
  • Still another object of the invention is to propose a method which makes it possible to produce such detergents easily and at low cost.
  • compositions having bon orthodialkyl benzene sulfonates by a new process which assures very satisfactory selectivity and yield.
  • another object of the invention is an economical process of manufacturing compositions having biodegradable, detergent properties, said method being characterized by subjecting normal-paraffin hydrocarbons having a number of carbon atoms of between 14 and 24, terminal atoms included, to passage in a reactor or furnace in the presence of hydrogen over a nonisomerizing cyclicizing dehydrogenation catalyst; isolating the single-ring aromatic products obtained; sulfonating them; and neutralizing the resultant sulfonic acids by means of a base.
  • the normal-paraffin hydrocarbons which serve as starting products can be obtained by passing a distillation stream or cut rich in normal paraffins over a molecular sieve.
  • the nonisomerizing cyclicizing dehydrogenation reaction can be carried out in the presence of hydrogen; upon entrance into the reactor, the molar ratio of hydrogen to normal-paraffin hydrocarbons is between 0.1
  • the temperature therein is within the range of 350C 500C; the temperature depends on the catalyst used and will be given hereafter.
  • dehydrogenation there is a formation of normal olefins, a certain amount of diolefins and aromatic products.
  • the catalyst must be a nonisomerizing cyclicizing dehydrogenation catalyst.
  • Pt-Li-As on alumina support is a suitable composition.
  • Other, suitable and inert supports may be employed with the disclosed catalysts.
  • the single-ring dialkyl aromatic hydrocarbons formed may be extracted in the condensed fraction by suitable means, for instance by passage through molecular sieves, by adsorption over alumina or silica gel or by liquid-liquid extraction by means of a selective solvent.
  • the single-ring aromatic fraction collected is composed practically exclusively of saturated straight-chain orthodialkyl benzenes the sum of the number of carbon atoms in the dialkyl chains of which is between 8 and 18, terminal atoms included, when the initial normal paraffin has a number of carbon atoms of between 14 and 24, terminal carbon atoms included.
  • the aromatic fraction is subjected to a sulfonation which may be carried out with sulfuric anhydride (S0 diluted in an inert gas such as nitrogen.
  • S0 sulfuric anhydride
  • the sulfonic acids obtained are then neutralized by a base, for instance soda or ammonia.
  • a base for instance soda or ammonia.
  • the resultant sulfonates are then dried.
  • the products of the invention comprise a group of compositions formed primarily of orthodialkyl benzene sulfonates the hydrocarbon chains of which are saturated and straight and which may be represented by the following formula:
  • n is the number of carbon atoms which the initial normal paraffin contains; n is between 14 and 24, terminal atoms included.
  • the accompanying drawing is a diagram which illustrates the two principal stages of the process of the invention, namely the dehydrocyclization of a normal paraffin and the extraction of the orthodialkyl benzenes.
  • a fresh normal paraffin having a number of carbon atoms of between 16 and 20, terminal carbon atoms included, which arrives through the line 1 is mixed with recycled products consisting essentially of paraffins and olefins coming from the line 2.
  • This mixture is diluted with hydrogen coming from the line 3 in such a manner that the molar ratio of hydrogen to the normal-paraffin hydrocarbons is close to one.
  • the mixture obtained is introduced at the top of a vertical reactor 4 brought to a temperature of between about 350C and 450C.
  • the reactor contains a catalyst consisting of chromium oxide and potassium oxide deposited on alumina in proportions by weight, measured with respect to the alumina, of 2.5 percent for the chromium and 2.2 percent for the potassium.
  • the rate of flow of the normal paraffin measured per unit of reactor volume per hour is between 0.5 and 2.5.
  • the products of the dehydrocyclization reaction are recovered in a receiver 5 where the separation of the gases and the liquids takes place.
  • the gases which are composed primarily of hydrogen and cracking products are evacuated through the line 6; the liquids through the line 7 arrive at an extraction column-8 which is filled, for instance, with silica gel.
  • Elution with npentane introduced through the line 9 makes it possible to collect via the line 11 the paraffins and olefins which may be recycled; such as, by feeding these to reactor 4 via line 2; further elution with ethyl ether introduced via line makes it possible to recover the aromatic products via the line 12.
  • the latter consist practically entirely of orthodialkyl benzenes with straight saturated hydrocarbon chains the total of the numbers of carbon atoms of which is between 10 and 14, terminal carbon atoms included, depending upon the normal paraffin initially introduced.
  • the invention is furthermore illustrated by the following examples, which are not of a limitative nature.
  • EXAMPLE I A stream of normal hexadecane and hydrogen is passed for 6 hours over a dehydrogenation catalyst consisting of chromium oxide and potassium oxide deposited on alumina, the chromium content being 2.5 percent by weight and the potassium content 2.2 percent by weight, both measured with respect to the alumina. The temperature is maintained at 425C. The rate of flow of the hexadecane is 2 v/v/hr and the molar ratio of hexadecane to hydrogen is 1.
  • the product is neutralized while cold and then decanted.
  • the aqueous phase is treated under reflux with an excess of soda for 1 hour.
  • the organic phase is treated in the same manner with an excess of soda under pressure at 160C for 1 hour.
  • the two aqueous phases are combined, the excess of soda is neutralized with sulfuric acid and thereupon evaporated until obtaining a dry product which is composed primarily of C sodium orthodialkyl benzene sulfonates the hydrocarbon chains of which are straight and saturated.
  • the detergent properties of the product obtained were compared with those of a current commercial soap by means of the following test.
  • the current commercial soap is of the following composition: sodium salts of fatty acids.
  • washings of a fabric impregnated with a standard soiling were carried out in a Launderometer" under the following conditions: washing of a sample of 5 g of fabric in 2 liters of solution for 30 minutes at C with agitation with 10 stainless steel balls of about 6 mm in diameter.
  • a microorganism culture was prepared with constant aeration at a temperature of 25C in a semisynthetic medium containing 20 mg per mil of the product to be tested; thereupon at the end of this time, the same quantity of detergent was again introduced and the test continued until the th day.
  • analyses were made so as to note the elimination of the products and thus their biodegradability.
  • the culture broth used in the tests comprises between 2 and 4 X 10 microorganisma per mm. It was prepared by aerobic fermentation in a nutrient medium rich in microorganisms taken from the water of the Seine River at the point of discharge of the large sewer of Clichy in Paris.
  • the detergent content of the cultures of microorganisms is determined in accordance with the method of Longwell and Maniece, the principle of which is as follows: acolored complex is formed with methylene blue; it is extracted with chloroform and a colorimetric measurement made by comparison with a standard product.
  • the biodegradation rate T at the end of 7 days is given by the following formula:
  • EXAMPLE 11 The paraffins and olefins coming from the line 111 in the accompanying diagram were passed over the catalyst described in Example I and mixed via line 2 with 33.5 grams of fresh n-hexadecane, namely a total of 169.0 grams of paraffin-olefin mixture passing into the reactor after mixture with hydrogen.
  • the rate of flow of the total charge is 2 v/v/hr, the temperature is 425C and the molar ratio of hydrogen to hydrocarbon is 1; the time of passage is 1 hour.
  • EXAMPLE 111 A stream of normal hexadecane and hydrogen is passed for one hour over the catalyst used in Example 1, heated to 440C. The rate of flow of the normal hexadecane is maintained equal to g/hr, the v/v/hr of the normal hexadecane is established at 1.0. The rate of flow of hydrogen is 10.6 liters per hour.
  • the sum of the weights of the cracking products, the dehydrogenation hydrogen and the carbon formed represents 1.4 gram.
  • Example I The treatment described in Example I applied to the liquid phase produces 75.0 grams of normal hexadecane, 13.6 grams of olefins and 10 grams of aromatic products very rich in C orthodialkyl benzenes with straight saturated hydrocarbon chains.
  • the sulfonic acids are neutralized by the method described in Example 1.
  • the mixture contains primarily C sodium orthodialkyl benzene sulfonates with saturated straight hydrocarbon chains; the mixture has good detergent and biodegradable properties.
  • EXAMPLE IV A stream of n-hexadecane and hydrogen is passed for 2 hours over a dehydrogenation catalyst composed of chromium, copper and potassium on alumina, these metals having been deposited in the form of nitrates, so that after calcination at 800C there is 4.97 percent by weight chromium, 3.03 percent copper and 1 percent potassium, measured with respect to the alumina.
  • the temperature is maintained at 425C; the rate of flow of hexadecane is l v/v/hr and the molar ratio of hydrogen to hexadecane is 1.
  • EXAMPLE V A mixture of n-hexadecane and hydrogen is passed for 2 hours over a catalyst consisting of platinum deposited on alumina.
  • the catalyst comprises 0.75 percent by platinum, referred to the alumina, and also 0.5 percent lithium and 0.09 percent arsenic.
  • the temperature being maintained at 400C, the rate of flow of the hexadecane being 1 v/v/hr, and the molar ratio of hydrogen to hexadecane being 1.0, there are collected for grams of n-hexadecane introduced 69.0 grams of unconverted hexadecane, 12 grams of aromatics, including 7.4 grams of orthodialkyl benzenes, and 12.6 grams of olefins. During the dehydrogenating reaction there is not noted any structural isomerization of the olefin and the alkyl benzenes recovered have only straight chains.
  • a process for preparing ortho-dialkyl benzenes which comprises:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00022337A 1969-03-26 1970-03-24 Ortho dialkyl benzene preparation via dehydrocyclization process Expired - Lifetime US3761532A (en)

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Application Number Priority Date Filing Date Title
FR6908911A FR2036620A5 (enrdf_load_stackoverflow) 1969-03-26 1969-03-26

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US (1) US3761532A (enrdf_load_stackoverflow)
BE (1) BE747035A (enrdf_load_stackoverflow)
DE (1) DE2014778A1 (enrdf_load_stackoverflow)
FR (1) FR2036620A5 (enrdf_load_stackoverflow)
GB (1) GB1256819A (enrdf_load_stackoverflow)
NL (1) NL7004111A (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5646047A (en) * 1993-10-20 1997-07-08 Powertech Labs Inc. Method and reagent kit for determining paper degredation in transformers

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB107283A (en) * 1916-08-03 1917-06-28 George Edward Seymour Improved Construction of Transporter, Truck or the like.
GB534236A (en) * 1939-09-07 1941-03-03 Bataafsche Petroleum A process for the catalytic cyclisation of aliphatic hydrocarbons
US2321006A (en) * 1939-03-21 1943-06-08 Standard Oil Co Conversion of nonbenzenoid hydrocarbons to aromatics
US2394170A (en) * 1940-01-08 1946-02-05 Universal Oil Prod Co Treatment of hydrocarbons
CA546029A (en) * 1957-09-10 Krekeler Hans Process for preparing aromatic hydrocarbons
US2962536A (en) * 1958-04-09 1960-11-29 Atlantic Refining Co Production of polycyclic aromatic hydrocarbons from high molecular weight paraffins
US3291755A (en) * 1966-02-14 1966-12-13 Universal Oil Prod Co Catalytic dehydrogenation catalyst for paraffinic hydrocarbons
US3296324A (en) * 1962-08-20 1967-01-03 Chevron Res Dehydrocyclodimerization of low molecular weight paraffins
US3297773A (en) * 1962-12-04 1967-01-10 Standard Oil Co Manufacture of aromatic hydrocarbons
US3360586A (en) * 1966-07-26 1967-12-26 Universal Oil Prod Co Catalytic dehydrogenation of paraffinic hydrocarbons mixed with trace h2o
US3361797A (en) * 1964-10-28 1968-01-02 Universal Oil Prod Co Process for producing a detergent
US3374281A (en) * 1965-09-28 1968-03-19 Chevron Res Production of alkylated benzenes from paraffins
US3501542A (en) * 1968-02-29 1970-03-17 Gulf Research Development Co Dehydrocyclization process

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA546029A (en) * 1957-09-10 Krekeler Hans Process for preparing aromatic hydrocarbons
GB107283A (en) * 1916-08-03 1917-06-28 George Edward Seymour Improved Construction of Transporter, Truck or the like.
US2321006A (en) * 1939-03-21 1943-06-08 Standard Oil Co Conversion of nonbenzenoid hydrocarbons to aromatics
GB534236A (en) * 1939-09-07 1941-03-03 Bataafsche Petroleum A process for the catalytic cyclisation of aliphatic hydrocarbons
US2394170A (en) * 1940-01-08 1946-02-05 Universal Oil Prod Co Treatment of hydrocarbons
US2962536A (en) * 1958-04-09 1960-11-29 Atlantic Refining Co Production of polycyclic aromatic hydrocarbons from high molecular weight paraffins
US3296324A (en) * 1962-08-20 1967-01-03 Chevron Res Dehydrocyclodimerization of low molecular weight paraffins
US3297773A (en) * 1962-12-04 1967-01-10 Standard Oil Co Manufacture of aromatic hydrocarbons
US3361797A (en) * 1964-10-28 1968-01-02 Universal Oil Prod Co Process for producing a detergent
US3374281A (en) * 1965-09-28 1968-03-19 Chevron Res Production of alkylated benzenes from paraffins
US3291755A (en) * 1966-02-14 1966-12-13 Universal Oil Prod Co Catalytic dehydrogenation catalyst for paraffinic hydrocarbons
US3360586A (en) * 1966-07-26 1967-12-26 Universal Oil Prod Co Catalytic dehydrogenation of paraffinic hydrocarbons mixed with trace h2o
US3501542A (en) * 1968-02-29 1970-03-17 Gulf Research Development Co Dehydrocyclization process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J. L. Ernst, The Oil and Gas Journal, 64, 112 115 (1966). *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5646047A (en) * 1993-10-20 1997-07-08 Powertech Labs Inc. Method and reagent kit for determining paper degredation in transformers

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Publication number Publication date
FR2036620A5 (enrdf_load_stackoverflow) 1970-12-24
GB1256819A (enrdf_load_stackoverflow) 1971-12-15
BE747035A (fr) 1970-09-09
NL7004111A (enrdf_load_stackoverflow) 1970-09-29
DE2014778A1 (de) 1970-10-01

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