US2644827A - Manufacture of tetraethyllead - Google Patents

Manufacture of tetraethyllead Download PDF

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Publication number
US2644827A
US2644827A US244514A US24451451A US2644827A US 2644827 A US2644827 A US 2644827A US 244514 A US244514 A US 244514A US 24451451 A US24451451 A US 24451451A US 2644827 A US2644827 A US 2644827A
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United States
Prior art keywords
ethylation
solids
liquid
tetraethyllead
alloy
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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
Application number
US244514A
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English (en)
Inventor
Clarence M Neher
Frank L Padgitt
Paul E Weimer
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Ethyl Corp
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Ethyl Corp
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Filing date
Publication date
Priority to NL86974D priority Critical patent/NL86974C/xx
Priority to NLAANVRAGE7202485,B priority patent/NL171479B/xx
Application filed by Ethyl Corp filed Critical Ethyl Corp
Priority to US244514A priority patent/US2644827A/en
Priority to FR1134292D priority patent/FR1134292A/fr
Priority to GB887/51A priority patent/GB712644A/en
Priority to DEE5671A priority patent/DE940297C/de
Application granted granted Critical
Publication of US2644827A publication Critical patent/US2644827A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/24—Lead compounds

Definitions

  • This invention relates to the manufacture of tetraethyllead. Morep'articularly, the invention relates to a new and improved process whereby 6 Claims. (01. 260-437) tetraethyllead is manufactured by the ethylation of an active formof lead in a continuous manner.
  • Tetraethyllead may be synthesized by a num' ber of reactions, a preferred procedure involving the ethylation'of an alloy of lead and an alkali metal at'elevatedtemperature with anethylating agent. Typical'of such operations is the ethylathat it is a batch operation and therefore sub-- ject to all the usual limitations of a batch operas 1 tion.
  • the pressure is controlled by the rate of feed of the ethyl chloride.
  • the autoclave cha'rgeis maintained at the elevated temperature and'pressure for fur]- ther reaction.v
  • Excess ethyl chloride is then vaporized from the autoclave charge, the vaporization being facilitated by circulation of heating medium through a jacket on the autoclave.
  • reaction mass containingexcess metallic lead, tetraethyllead
  • the ethyl chloride is fed 7 in the ratio of about one-half part 35, and sodium chloride, and minor amounts of sodium or sodium-lead alloy.
  • the reaction mass is discharged to a steam still, wherein it is first immersed in water and then by weight to one part of sodium-lead alloy.
  • An object of the presentinvention is to provide a new and improved process capable of eflicient continuous operation in the manufacture of tetraethyllead. Another important object is to assure high yields of tetraethyllead. An additional object is to'virtually negate the possibilityiof de composition of the tetraethyllead in the ethylation zone, and also to provide an ethylatedmixture particularly susceptible to efficient recovery of the tetraethyllead therefrom. Yet another object is to provide a high production rate in terms of tetraethyllead produced per unit volume of reaction space.
  • the invention comprises the ethylation of the lead of an alloy of lead and an alkali metal with a liquid ethylating agent, in the presence of a substantial excess of the ethylating agent.
  • the mitxure of components, or ethyla tion mixture is stirred or agitated under nonideal conditions; that is, the agitation is appr'e c'iably short of that required to provide uniform or ideal distribution of solids throughout theethylation mixture.
  • the solids in the ethylation zone are non-uniformlydistributed, nevertheless a high fraction of about percent or more are suspended by virtue of the agitation and'all solids are in vigorous motion.
  • the liquid proportions at all points is such of lead which is a large component cfthe ethylation mixture solids.
  • the tetraethyllead product is uniformly distributed through the predominantly ethyl chloride liquid phase.
  • the liquid phase does not show a composition gradient even when the lead containing alloy is fed cyclically.
  • cyclically is meant that the ethylation is carried out continuously but the alloy is fed intermittently in.
  • FIG. 1 is a diagrammatic representation of apparatus for a preferred and easily operable embodiment of the process.
  • the principal unit of apparatus is the ethylation vessel or ethylator l.
  • the usual auxiliary equipment includes an ethyl chloride supply tank 2 and feed line 3, and an alloy supply hopper '4 fitted with lines 43, M, for maintaining an inert gas atmosphere in contact with the alloy.
  • a feed column 5, which can be blocked off by valves 6,1 provides a pressurized feed chamber from which the-comminuted alloy can be dropped into the feedend of conveyer 8. Provision is made for pressure blanketing of the alloy in feed chamber 5 by inert gas lines 45, 4B.
  • a drive motor 9 powers the conveyer, which transports the alloy into the ethylator I at the top, that is into a vapor space.
  • the ethyl chloride feed rate through line 3 is controlled by valve 10, a flow meter ll providing visual check on the rate of flow.
  • nozzle line I32 can be used for the discharge by opening valve I42.
  • a bottom discharge line I! discharges solids, which include lead metal and alkali metal chlorides, to subsequent operations Removal of the 1 for the recoveryofmetal values.
  • liquid phase from the solids-liquid separator "is accomplished through line IS, the flow rate to the tetraethyllead concentration apparatus l9 being;
  • the concentration unit I9 may take several different forms, a preferred- Agitation elements within the ethylator inthe ethylator through line 42 for cleanout.
  • allows draining During operation, the level of the ethylation mixture is asce'rtainablefrom a liquid level gauge 40.
  • the alloy feed apparatus will consist simply of a. molten alloy supply tank and a feed line and nozzle for passing the liquid alloy to the ethylation zone.
  • the solids-liquid separator 16 may utilize any of several different unit operations.
  • the ethylated slurry is susceptible of filtration, so that the solids-liquid separator can be a continuous filter of types available.
  • a solvent such as naphtha, benzene, or preferably, an alkyl chloride.
  • Ethyl chloride itself is a highly effective solvent for the tetraethyllead.
  • the solids-liquid separator can be an extraction operation in which the liquid phase is dissolved in ethyl chloride and separated from the solids with high efliciency.
  • Example 1 The ethylator I was charged with ethyl chloride through line I0. Hot water was circulated to the jacket 23 through line 24 until the charge was at a temperature of C. Monosodiumlead alloy, in the form of thin flakes, which had been'previously charged to the alloy feed column 5 was then charged by opening valve 1 and operating feed conveyer 8. Agitation of the charge wasstarted immediately before alloy fiow was started, the speed of rotation providing a peripheral velocity of 660 feet per minute.
  • ethyl chloride and sodium-lead alloy were fed at the weight ration of 5.0:1.0, ethyl chlorideralloy, corresponding to an excess of approximately 1700 percent of the ethyl chloride theoretically required.
  • the volumetric feed rates in'terms of pounds per hour per cubic foot of ethylation zone, amounted to 6.5 pounds of sodium-lead alloy.
  • a particular virtue of the process is that the residence time of the solid components of the ethylation mixture can be controlled at will and to some extent independently of the feed ratioof the ethylating liquid and the solids.
  • the ethylation mixture can be main-- tained with an appreciably high solids content and the. benefits of an extended residence time attained.
  • Theupper-limit of the preferred range is a liquid solid'ratio of 5:1. Operation below this range, in conjunction with the non-ideal agitation which is a characteristic of the process, results in mechanie cal attrition of the solids'p'articles, which, being largely metallic lead, are susceptible to mechanical fusion to form masses which can bind the agitator operation.
  • non-ideal agitation of the ethylation mixture is an essential characteristic of the process.
  • sufficient agitation powerinput, efiicientlyused is requiredto maintain all the solids present discretely dispersed in the liquid phase.
  • efficient agitation is meantthat the mechanical horsepower input of the agitator assembly is distributed to various strata in the'ethylation zone according to methods frequently used.
  • agitation sweep area varying 'fromabout 10 to about 60 percent of the ethylation zone cross sectional area.
  • agitating elements which can be either propellers or turbine agitators, which sweep at least 40 percent of the ethylation zone cross sectional area.
  • the lower ranges are avoided as higher radial speeds are- In prior ethylations,
  • the lowermost element should be appreciably closer to the bottom of the ethylation zone than is common practice.
  • the lowermost turbine or propeller is within a distance of from one-fourth to one-half of its diameter to the bottom of the zone.
  • a total depth of ethylation mixture of at least several feet, and up to about four feet, will be employed.
  • a plurality of agitating elements is customarily provided.
  • a desirable vertical disposition of such plural elements is at space intervals of about one-half to threefourths of the diameter of such elements.
  • the power requirements of the process will of course depend to some extent on the mechanical losses in the drive mechanism and similar mechanical devices, such as the gland or seal at which. the agitator shaft enters the enclosed ethylation zone. Measurement of such losses, however, has shown the actual horsepower requirements to the agitator shaft. Surprisingly, the minimum horsepower requirements did not vary with a reduction in liquid solid ratio in the range of 4:1 to 2:1, but satisfactory agitation was achieved with a power input of approximately 0.1 horsepower per cubic foot of ethylation zone. As a general rule, power inputs of over 0.5 horsepower per cubic foot are avoided in order to assure the non-uniform distribution of solids essential to the process.
  • a significant feature of the process is the control of the residence time of the solids within the ethylation zone. This is achieved by the removal or discharge of a product slurry at a point remote from the bottom of the ethylation vessel, which in turn takes advantage of the effects of the non-ideal agitation employed. It has been found that by non-uniform distribution of the solids, a segregation both in terms of weight concentration and in terms of chemical composition is attained.
  • slurry samples were removed from an ethylator operated similarly to that described in the working example.
  • the samples were removed at the bottom and at the midpoint, that is, at a point corresponding to 50 percent of the total depth of the ethylation mixture.
  • the liquid solid ratios at the bottom and midpoint were 1.6:1 and 4.9:1, respectively. Analyses of the solids in these samples also showed that the ethylation was only '79 percent complete at this point but was 8'7 percent complete at the midpoint.
  • the solids in the product slurry contained a lower proportion of unreacted solids than either of the foregoing samples.
  • the process is not limited to a specific ethylation reaction, but is applicable to ethylation reactions involving sodium-lead alloys of relatively high sodium content.
  • the process is applicable in the ethylation of alloys of the composition corresponding to the formula NazPb, or with lesser and greater proportions of sodium.
  • alloys with other alkali metal comonents are suitable feed components and similar benefits will be realized.
  • alloys containing potassium, either as the sole alkali metal, or as a component of a ternary alloy can be advantageously ethylated by the process.
  • ethyl chloride is the preferred ethylating agent
  • other ethylating agents may be substituted for the ethyl chloride and the benefits of the method will be realized, although in varying degree.
  • Examples of alternative ethylating agents which can thus be substituted for the ethyl chloride are ethyl bromide, ethyl iodide, and diethyl sulfate.
  • ethyl chloride will be most widely used owing to the cheapness and availability of this chemical.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Manufacture And Refinement Of Metals (AREA)
US244514A 1951-08-31 1951-08-31 Manufacture of tetraethyllead Expired - Lifetime US2644827A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
NL86974D NL86974C (de) 1951-08-31
NLAANVRAGE7202485,B NL171479B (nl) 1951-08-31 Steunelement voor het ondersteunen van een uit een aantal met elkaar verbonden bouwelementen gevormde draag- of steunconstructie.
US244514A US2644827A (en) 1951-08-31 1951-08-31 Manufacture of tetraethyllead
FR1134292D FR1134292A (fr) 1951-08-31 1952-01-10 Perfectionnements à la fabrication du plomb tétraéthyle
GB887/51A GB712644A (en) 1951-08-31 1952-01-11 Improvements in or relating to manufacture of tetraethyllead
DEE5671A DE940297C (de) 1951-08-31 1952-06-26 Kontinuierliches Verfahren zur Herstellung von Bleitetraaethyl

Applications Claiming Priority (1)

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US244514A US2644827A (en) 1951-08-31 1951-08-31 Manufacture of tetraethyllead

Publications (1)

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US2644827A true US2644827A (en) 1953-07-07

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US244514A Expired - Lifetime US2644827A (en) 1951-08-31 1951-08-31 Manufacture of tetraethyllead

Country Status (5)

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US (1) US2644827A (de)
DE (1) DE940297C (de)
FR (1) FR1134292A (de)
GB (1) GB712644A (de)
NL (2) NL86974C (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2777866A (en) * 1953-08-17 1957-01-15 Ethyl Corp Recovery of tetraalkyl-lead compounds
US2777867A (en) * 1953-08-03 1957-01-15 Ethyl Corp Recovery of alkyllead compounds
US2856419A (en) * 1953-04-15 1958-10-14 Ethyl Corp Manufacture of tetraethyllead

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2091114A (en) * 1934-10-27 1937-08-24 Du Pont Process of making tetra-alkyl lead
FR963005A (de) * 1947-03-11 1950-06-28

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2091114A (en) * 1934-10-27 1937-08-24 Du Pont Process of making tetra-alkyl lead
FR963005A (de) * 1947-03-11 1950-06-28

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2856419A (en) * 1953-04-15 1958-10-14 Ethyl Corp Manufacture of tetraethyllead
US2777867A (en) * 1953-08-03 1957-01-15 Ethyl Corp Recovery of alkyllead compounds
US2777866A (en) * 1953-08-17 1957-01-15 Ethyl Corp Recovery of tetraalkyl-lead compounds

Also Published As

Publication number Publication date
FR1134292A (fr) 1957-04-09
GB712644A (en) 1954-07-28
NL171479B (nl)
NL86974C (de)
DE940297C (de) 1956-03-15

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