US2349458A - Reaction of paraffinic hydrocarbons - Google Patents

Reaction of paraffinic hydrocarbons Download PDF

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Publication number
US2349458A
US2349458A US242572A US24257238A US2349458A US 2349458 A US2349458 A US 2349458A US 242572 A US242572 A US 242572A US 24257238 A US24257238 A US 24257238A US 2349458 A US2349458 A US 2349458A
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reaction
alkylation
catalyst
reactants
liquid
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US242572A
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John J Owen
Eldon E Stahly
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Standard Oil Development Co
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Standard Oil Development Co
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Priority to FR851032D priority patent/FR851032A/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/26—Chromium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
    • C07C2527/054—Sulfuric acid or other acids with the formula H2Sn03n+1
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/08—Halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/08—Halides
    • C07C2527/10—Chlorides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
    • C07C2527/126—Aluminium chloride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/128—Compounds comprising a halogen and an iron group metal or a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/132—Compounds comprising a halogen and chromium, molybdenum, tungsten or polonium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/133—Compounds comprising a halogen and vanadium, niobium, tantalium, antimonium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/135—Compounds comprising a halogen and titanum, zirconium, hafnium, germanium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/138—Compounds comprising a halogen and an alkaline earth metal, magnesium, beryllium, zinc, cadmium or mercury

Definitions

  • This invention relates to improvements in the production of highly desirable components of motor fuels and pertains particularly to the production of relatively low boiling saturated aliphatic hydrocarbons which have been found to be useful in the production of gasolines.
  • a saturated branched chain normally liquid paramn may be produced directly by alkylating a normally gaseous branched chain parafin, for example, isobutane, by treating such a compound with a normally gaseous mono-olefin without the necessity of including a subsequent hydrogenation treatment in the process as would be the case where a polymerization process had been used.
  • a normally gaseous branched chain parafin for example, isobutane
  • alkylation is a distinct advance in the art.
  • Large supplies of field butanes, refinery C4 cuts from cracking units, debutanizer units, etc., each containing substantial quantities of gaseous olefins and parafflns both straight and branched chain are available.
  • Such gaseous mixtures have heretofore been fed to polymerization processes which are able to utilize only the olefinic content of the mixtures.
  • reaction conditions which have been found to be particularly efiective in promoting the desired reaction. It is obvious that the optimum reaction conditions will vary for each particular catalyst employed. In general, it may be said that reaction conditions are favored when the feed rates are adjusted to provide longer contact time than would be used in corresponding polymerization reactions. Production of saturated hydrocarbons was also noticeably favored. b more intimate contact between the reactants.
  • the feed stock therefore is preferably introduced into the reaction zone through jets, porousthimbles, turbomixers and the like.
  • the invention is not limited to the use of reactants from an particular source.
  • Single hydrocarbons may be employed, such as isobutane, isopentane, etc.
  • mixtures of hydrocarbons containing the essential parafllnic constituents As the normally gaseous paraflins used, the butanes and pentanes may be employed. Where the liquid paraifin used is a straight chain compound, then branched chain pentanes and/or isobutane or mixtures containing at least one of them are usually employed.
  • Field butanes may be used directly or may be used after first having been subjected to a catalytic polymerization or alkylation reaction to remove substantially all of their olefinic content.
  • refinery C3-C5 and C4 cuts after being treated to alkylating or polymerizing conditions, having had their olefinic content substantially depleted are suitable sources of supply of the gaseous paraflins used as reactants in the present inventions process.
  • the normally liquid parafllns used may be e ther straight or branched chain compounds, but at least one of the reactants should be a branched chain compound, preferably a compound containing a tertiary carbon atom where the other employed is a straight chain hydrocarbon.
  • both types of reactants may contain tertiary carbon atoms in their molecules although the reaction of other branched chain compounds is contemplated.
  • Paraflins ranging from the hexanes to the dodecanes either as single chemical compounds or as mixtures with others of the same homologous series or admixed with inert compounds may be used as reactants in the process of the present invention. Mixtures of branched chain and straight chain liquid parafflns may be satisfactorily employed. Thus isooctane and normal heptane may be employed together with isobutane as a suitable reaction mixture. Isododecane, isobutane and butane: isodecane and isopentane; etc. are suitable reaction mixtures as well.
  • a preferred mixture for use as the liquid paraiiinic reactant of the present invention is obtained from the catalytic alkylation of isobutane with isobutylene, its polymers, copolymers, etc.. separation of the desired gasoline fraction and the isolation of the C9 and heavier fraction, for use in the present invention.
  • the following may serve as the liquid parafiins useful in the reaction although it is to be distinctly understood that this enumeration is but representative and it is not intended that the operation of the invention be restricted to these compounds or mixtures containing these-me.
  • 2,4 dimethyl pentane, 2,2 dimethyl pentane, 3,3 dimethyl pentane, and higher homologues' may be used either separately or in mixtures of one or more.
  • the'invention is directed to the use of liquid hydrocarbons containing a total of six or more carbons in each molecule and of low octane values and their normally liquid isomers.
  • the invention contemplates the use of halides of metals such as aluminum, zinc. antimony, tin, iron, nickel, tungsten, tantalum, zirconium, molybdenum, etc., specifically the chlorides and bromides of these metals or mixtures'oi these, or mixed with small amounts for example, between about 2.2 and about 11.5% by weight based on the feed stock, of an alkyl halide such as ethyl chloride, propyl chloride, tertiary butyl chloride, tertiary or secondary amyl chloride, the bromides thereof, etc.
  • the ethyl halides promote the activity Of these catalysts, their effect being to increase the formation of lower boiling saturates at the expense of higher boiling paraiiins.
  • Another particularly desirable catalyst is the metal halide-aluminum halide complex wherein the aluminum halide is present in from about 0.5 to about 2.5 moles per mol of other metal halide.
  • AlCls-NaCl in varying molecular proportions has been found to be a particularly effective catalyst.
  • a catalyst .composed of KBr-FeCls complex has been very effective in promoting alkylation.
  • Other similar double salt complexes which are Within the scope of the invention are lithium chlor aluminate, antimony brom aluminate, sodium brom aluminate, mercury brom aluminate, potassium chlor aluminate, etc, each in the varying molar ratios above designated.
  • These complex double salts may be prepared by mixing the alkali metal halide, alkaline earth metal halide or other corresponding metal halide, for example, sodium chloride, with slightly more aluminum halide, for example, aluminum chloride, than is necessary for the catalyst of the desired mol ratio.
  • the excess aluminum chloride is added in order to compensate for losses due to volatilization on heating.
  • the mixture is heated in an open vessel until fusion occurs and a clear liquid results. At a temperature of 400-450 F. some solid sodium chloride usually is present and the liquid portion of the mixture is therefore poured oil through a wire gauze.
  • Another catalyst found to be highly useful in the process of the present invention is concentrated sulfuric acid. It is preferred to use this catalyst in concentrations of between about '70 and usually about 96-98% concentration.
  • Organic metallic compounds, such as methyl aluminum chloride and dimethyl aluminum chloride are also suitable catalysts for the reaction.
  • Suitable aluminous and/or siliceous carriers are activated alumina, silica gel, bauxite, fuller's earth, bentonite, lrieselguhr, pumice, celite, Sil- O-Cel, infusorial earth, montmorillonite, Marsll clays, Tonsil, Super Filtrol, activated Floridin, etc. These substances not only serve as excellent carriers for alkylation catalysts, but in many instances, they serve as highly useful catalysts when used alone.
  • Clays oi the bentonite and montmorllionite type acid activated according to the process of Chappell et al. U. 8. Patent 1,642,871, September 20, 1927, are particularly desirable. Clays have also been found to be advantageously used when they contain small-percentages of allryl halides, for example, tertiary butyl chloride.
  • any suitable reactivation or regeneration process may be employed, for example, treatment 01' the catalyst mass with inorganic acidic gases such as the hydrogen halides, HCl, I-IBr, or the free halogen, C12 and Br: or by treatment with heat and pressure to free the pores of the catalyst mass of residual heavier hydrocarbon compounds and decomposition residues that accumulate during the alkylation process.
  • inorganic acidic gases such as the hydrogen halides, HCl, I-IBr, or the free halogen, C12 and Br: or by treatment with heat and pressure to free the pores of the catalyst mass of residual heavier hydrocarbon compounds and decomposition residues that accumulate during the alkylation process.
  • Such a process of reactivation is also applicable in the cases where activated clays or catalytically impregnated activated clays are used.
  • the reaction may be carried out at temperatures ranging from between about F. to about 550 F. and under pressure ranging from between about atmospheric to about 3000 lbs/sq. in, gauge and at a throughput of between 0.5 and about 7.0 volumes/volume of catalyst/hour.
  • the reaction may be materially assisted it a dehydrogenation catalyst is admixed with the alkylation catalyst.
  • a dehydrogenation catalyst is admixed with the alkylation catalyst.
  • Such catalysts as chromium oxide, chromium oxide-aluminum oxide, silica gels or precipitates impregnated with the salts of nickel.
  • chromium, aluminum, vanadium, or other dehydrogenating metals may be admixed with the alkylation catalysts in an amount between about 0.2% and about 25% of the total alkylation catalyst. It is, however, not advisable to mix such dehydrogenation catalysts with a strongly basic or strongly acidic alkylation catalyst, since it would obviously defeat the very purpose for which they are added to have such catalysts react with acids or alkalis to any appreciable extent.
  • Example 1 Into a continuous unit having a catalyst chamber holding 100 cc. of sodium chloride-aluminum chloride mixture made up in a ratio of 1 mol of NaCl to 1.8 mols of A1013, the mass being deposited on celite, there was introduced a feed stock consisting of 89.8% isobutane and 10.2% isooctane. This feed, while at 3000 lbs/sq. in. and at 400 F., was passed through the catalyst chamber at 3 volumes/volume of catalyst/hour continuously. The resulting product, after separation from the unreacted reactants, constituted 168% yield based upon the original isooctane in the feed stock, had a bromine number of 20, and contained by weight 0! saturates. It was fractioned into the following cuts: 22% Crimetion, 5% Ce fraction, 8% C1 fraction, 40% Cs fraction, and 25% Co and heavier fractions.
  • Example 2 Into a suitable pressure vessel 9. mixture of 88% isobutane and 12% isooctane was treated with a mixture of aluminum chloride containing 3.2% by weight 01' the total reactants of tertiary butyl chloride. The amount of catalyst used represented 14.1 grams per 100 grams of feed stock and only sufficient pressure was maintained to keep the reaction medium liquid at the reactive temperature of 15 F. After 4.5 hours had elapsed the reacted product was freed of unreacted reactants and the isolated product was obtained in a 74% yield based upon the weight of the isooctane treated. The product had a bromine number of 1 and was 99% saturated. It fractioned to 20% by weight of C-C1 cut, 70% Ca cut and Co and heavier hydrocarbon cut.
  • Example 3 Into a continuous unit having a catalyst chamber holding 100 cc. of sodium chloride-aluminum chloride mixture made up in a ratio of 1 mol of NaCl to 1.7 mols of AlCla deposited on celite, there was introduced a feed stock comprising 9.3% normal heptane and 90.7% of isobutane. This feed at 2000 lbs/sq. in. gauge and at 400 F. was passed through the catalyst chamber at 3 V./V./hour continuously. The resulting prodnet, after separation from the unreacted reactants. constituted 179% yield based upon the original heptane in the feed stock, had a bromine number of 27 and contained 85% by weight of saturates. It was fractionated into the following cuts or fractions: 50% C5C'1 fractions, 40% Ca fraction, and 10% Ca and heavier fractions. The final boiling point of the total product was 401 F.
  • a process for the production of a composition composed predominately of saturated normally liquid hydrocarbons boiling in the gasoline range .rhich comprises reacting isobutane with a relatively high molecular weight acyclic paraffin in the presence of a metal halide-aluminum halide double salt complex, wherein the metal is other than aluminum.
  • a process for the produ'ction of a composition composed predominately of saturated liquid hydrocarbons boiling within the gasoline range which comprises reacting isobutane with isooctane in the presence of NaClAlCh double salt complex supported on celite, the mol ratio of AlCl3 to NaCl being between about 1.1 and about 2.0 to 1, at a temperature between about 300 and about 500 F. at a pressure between about 1000 and about 3000 lbs./sq. in. gauge at a throughput of between about 0.5 and about 7.0 volumes/volume of catalyst/hour.
  • a process for the production of a composition composed predominantly of saturated, branched chain, normally liquid hydrocarbons boiling in the gasoline range which comprises reacting at least one low boiling isoparaflin with at least one normally liquid parafiin of difierent molecular weight than the low boiling isoparaflin, under alkylation reaction conditions in the presence of a metal halide-aluminum halide double salt complex wherein the metal is other than aluminum.
  • a process for the production of a composition composed predominantly of saturated, branched chain, normally liquid hydrocarbons boiling in the gasoline range which comprises reacting an isoparaflin of less than six carbon atoms per molecule with a. normally liquid paraflin of at least six carbon atoms per molecule under alkylation reaction conditions in the presence of a metal halide-aluminum halide double salt complex wherein the metal is other than aluminlim.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US242572A 1938-11-26 1938-11-26 Reaction of paraffinic hydrocarbons Expired - Lifetime US2349458A (en)

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US242572A US2349458A (en) 1938-11-26 1938-11-26 Reaction of paraffinic hydrocarbons
GB2690/39A GB524252A (en) 1938-11-26 1939-01-26 An improved manufacture of saturated aliphatic hydrocarbons boiling within the gasoline range
FR851032D FR851032A (fr) 1938-11-26 1939-03-01 Procédé de fabrication d'un produit d'addition aux carburants

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2943126A (en) * 1958-09-26 1960-06-28 Exxon Research Engineering Co Liquid catalyst paraffin alkylation process
US2965693A (en) * 1958-12-31 1960-12-20 Exxon Research Engineering Co Paraffin alkylation with surface active agents
US2966535A (en) * 1958-08-22 1960-12-27 Exxon Research Engineering Co Molybdenum promoted alkylation of paraffins
US2971037A (en) * 1958-12-01 1961-02-07 Exxon Research Engineering Co Gamma alumina promoted paraffin alkylation process
US2978524A (en) * 1958-12-01 1961-04-04 Exxon Research Engineering Co Paraffin alkylation process promoted with silica gel and aluminum bromide
US2982800A (en) * 1959-02-05 1961-05-02 Exxon Research Engineering Co Means for producing branched hydrocarbons
US2987561A (en) * 1959-03-04 1961-06-06 Exxon Research Engineering Co Method for producing isoparaffins
US2987562A (en) * 1959-05-18 1961-06-06 Exxon Research Engineering Co Catalyst recovery in hydrocarbon reactions promoted with aluminum bromide
US3000993A (en) * 1959-09-28 1961-09-19 Exxon Research Engineering Co Paraffin alkylation process
US3002038A (en) * 1959-07-28 1961-09-26 Exxon Research Engineering Co Reactivation of paraffin alkylation catalysts
US3002037A (en) * 1959-05-22 1961-09-26 Exxon Research Engineering Co Catalytic treatment of hydrocarbons in the presence of naphthenes
US3045056A (en) * 1958-11-03 1962-07-17 Exxon Research Engineering Co Supported catalyst paraffin alkylation process
US3097155A (en) * 1959-04-03 1963-07-09 Sinclair Research Inc Process for the conversion of paraffin hydrocarbons with isobutane utilizing hydrogen fluoride as a catalyst
US3136825A (en) * 1960-10-20 1964-06-09 Sinclair Research Inc Process for disproportionation of isoparaffinic hydrocarbons
US12228158B2 (en) 2017-12-15 2025-02-18 Phillips Screw Company Stick fit fastener recess system
US12551992B2 (en) 2016-07-11 2026-02-17 Phillips Screw Company Fastener system with stabilizer ribs and square drive
US12560193B2 (en) 2017-12-15 2026-02-24 Phillips Screw Company Stick fit fastener recess system

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2966535A (en) * 1958-08-22 1960-12-27 Exxon Research Engineering Co Molybdenum promoted alkylation of paraffins
US2943126A (en) * 1958-09-26 1960-06-28 Exxon Research Engineering Co Liquid catalyst paraffin alkylation process
US3045056A (en) * 1958-11-03 1962-07-17 Exxon Research Engineering Co Supported catalyst paraffin alkylation process
US2971037A (en) * 1958-12-01 1961-02-07 Exxon Research Engineering Co Gamma alumina promoted paraffin alkylation process
US2978524A (en) * 1958-12-01 1961-04-04 Exxon Research Engineering Co Paraffin alkylation process promoted with silica gel and aluminum bromide
US2965693A (en) * 1958-12-31 1960-12-20 Exxon Research Engineering Co Paraffin alkylation with surface active agents
US2982800A (en) * 1959-02-05 1961-05-02 Exxon Research Engineering Co Means for producing branched hydrocarbons
US2987561A (en) * 1959-03-04 1961-06-06 Exxon Research Engineering Co Method for producing isoparaffins
US3097155A (en) * 1959-04-03 1963-07-09 Sinclair Research Inc Process for the conversion of paraffin hydrocarbons with isobutane utilizing hydrogen fluoride as a catalyst
US2987562A (en) * 1959-05-18 1961-06-06 Exxon Research Engineering Co Catalyst recovery in hydrocarbon reactions promoted with aluminum bromide
US3002037A (en) * 1959-05-22 1961-09-26 Exxon Research Engineering Co Catalytic treatment of hydrocarbons in the presence of naphthenes
US3002038A (en) * 1959-07-28 1961-09-26 Exxon Research Engineering Co Reactivation of paraffin alkylation catalysts
US3000993A (en) * 1959-09-28 1961-09-19 Exxon Research Engineering Co Paraffin alkylation process
US3136825A (en) * 1960-10-20 1964-06-09 Sinclair Research Inc Process for disproportionation of isoparaffinic hydrocarbons
US12551992B2 (en) 2016-07-11 2026-02-17 Phillips Screw Company Fastener system with stabilizer ribs and square drive
US12228158B2 (en) 2017-12-15 2025-02-18 Phillips Screw Company Stick fit fastener recess system
US12560193B2 (en) 2017-12-15 2026-02-24 Phillips Screw Company Stick fit fastener recess system

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FR851032A (fr) 1940-01-02
GB524252A (en) 1940-08-01

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