US3164537A - Recovery of tetraalkyl lead from electrolytic reaction mixtures - Google Patents

Recovery of tetraalkyl lead from electrolytic reaction mixtures Download PDF

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US3164537A
US3164537A US79845A US7984560A US3164537A US 3164537 A US3164537 A US 3164537A US 79845 A US79845 A US 79845A US 7984560 A US7984560 A US 7984560A US 3164537 A US3164537 A US 3164537A
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lead
ether
overhead
high boiling
tetraalkyl
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US79845A
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Linsk Jack
Ralph W Carl
Field Edmund
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Standard Oil Co
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Standard Oil Co
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Priority to NL262356D priority Critical patent/NL262356A/xx
Priority to LU39891D priority patent/LU39891A1/xx
Priority to US35078A priority patent/US3118825A/en
Priority to US35441A priority patent/US3155602A/en
Priority to US67178A priority patent/US3298939A/en
Priority to US79845A priority patent/US3164537A/en
Application filed by Standard Oil Co filed Critical Standard Oil Co
Priority to FR855672A priority patent/FR1287026A/en
Priority to GB9445/61A priority patent/GB984421A/en
Priority to DEST17583A priority patent/DE1157616B/en
Publication of US3164537A publication Critical patent/US3164537A/en
Application granted granted Critical
Priority claimed from US457802A external-priority patent/US3399199A/en
Priority to US547780A priority patent/US3584050A/en
Priority to SE6606793A priority patent/SE375521B/xx
Priority to SE7011413A priority patent/SE379040B/xx
Priority to IL25803A priority patent/IL25803A/en
Priority to NO163070A priority patent/NO115641B/no
Priority to GB22126/66A priority patent/GB1142337A/en
Priority to DE1620004A priority patent/DE1620004C3/en
Priority to IT11441/66A priority patent/IT986753B/en
Priority to AT1227268A priority patent/AT314092B/en
Priority to AT481966A priority patent/AT288340B/en
Priority to FI661331A priority patent/FI51171C/en
Priority to BR179699/66A priority patent/BR6679699D0/en
Priority to BE681371D priority patent/BE681371A/xx
Priority to NL6606997.A priority patent/NL159975C/en
Priority to DK258666AA priority patent/DK125262B/en
Priority to FR62411A priority patent/FR1494137A/en
Priority to CH119169A priority patent/CH534121A/en
Priority to CH739566A priority patent/CH490318A/en
Priority to CH119269A priority patent/CH505551A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/06—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals
    • C07D295/067—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals with the ring nitrogen atoms and the substituents attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/24—Oxygen atoms attached in position 8
    • C07D215/26—Alcohols; Ethers thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/24—Oxygen atoms attached in position 8
    • C07D215/26—Alcohols; Ethers thereof
    • C07D215/28—Alcohols; Ethers thereof with halogen atoms or nitro radicals in positions 5, 6 or 7
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/04—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/32—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/13—Organo-metallic compounds

Definitions

  • Tetraalkyl lead compounds such as tetraethyl and tetramethyl lead are commercially important organometallic compounds. It has heretofore been discovered that tetraalkyl lead compounds such as these may be prepared by electrolyzing the corresponding alkyl Grignardreagent, c g., ethyl magnesium chloride, using a lead anode. By this process, alkyl groups in the lGrignard reagent are hydrocarbon is withdrawn; this is completely dry and is suitable for recycle to alkyl Grignard preparation. The bottoms from this distillation, containing tetraalkyl lead products, unreacted Grignard reagent, magnesium halide by-product, and high boiling ether, is hydrolyzed with v ether bottoms.
  • alkyl Grignardreagent c g., ethyl magnesium chloride
  • the major object of this invention is to provide a process for recovering tetraalkyl lead and solvent components from the aforementioned electrolytic reaction by a procedure which combines the simplicity of distillation with the solvent-conservingfeatures of hydrolysis. At the same time, Grignard attack on the ether is virtually completely prevented, and most of the solvent can be recovered in adry form suitable for recycle.
  • tetraalkyl lead is first manufactured by now-conventional electrolytic procedures, utilizing a lead anode and a solution of alkyl Grignard reagent in a solvent comprising excess alkyl halide, a high boiling'ether, tetrahydrofuran, and an aromatic hydrocarbon.
  • the electrolytic reaction mixture is subjected to a rst .low-temperature distillation.
  • a rst .low-temperature distillation may be advantageous to recycle a portion of the dry, high boiling ether-to this distillation step.
  • the aqueous phase is chiefly composed of magnesium halide, while the organic phase contains tetraalkyl lead and high boiling ether, possibly with al portion of unremoved aromatic hydrocarbon.
  • This organic phase is then redistilled either at subatmospheric pressure or in the presence of steam to separate a tetraalkyl lead overhead from the high boiling If this distillation employs steam, the ether may be dried by redistillation and then returned to electrolysis, while if subatmospheric pressure distillation is employed the bottoms per se are suitable for recycle.
  • the overhead from this distillation is tetraalkyl lead product, possibly containing a small amount of aromatic hydrocarbon, and may then be Withdrawn as the nal product of the inventive process.
  • the high boilingether may be any ether boiling above the boiling point of the particular tetraalkyl lead compound being manufactured.
  • ethers which may be used thosewhich are dialkyl ethers of an ethylene glycol, having at least two carbon atoms in each alkyl group and notmore than two ethylene groups in the glycol portion, are preferred, since the resultant electrolyte is able to preserve its homogeneity over a wide range of concentrations and temperatures.
  • exemplary glycol ethers are the diethyl ether of ethylene glycol, the dibutyl ether of ethylene glycol, the ⁇ diethyl ether of dethylene glycol, the dibutyl ether of diethylene glycol, and the hexylethyl ether of diethylene glycol.
  • Ethers other than those within the foregoing preferred class may also be used, and as examples of these there may be mentioned the dimethyl ether of diethylene glycol, the dimethyl ether of triethylene glycol, and various cyclic ethers, keeping inmind that the ether should boil higher than the tetraalkyl lead product (tetramethyl lead boils at C. and tetraethyl lead boils at about 195 C withdecomposition).
  • Aromatic hydrocarbons as'components of the electrolyte may be any of the aromatics which are liquidat room temperature and which are inert to Grignard reagents under conditions of the electrolysis.
  • Benzene and the alkyl benzenes such as toluene, the xylenes, cumene, the cymenes, etc. may be used, although it has been found that the simpler alkyl benzenes having only methyl groups offer some advantages with respect to low boiling points and high stability.
  • the overall electrolyte composition may be varied over wide ranges, depending upon desiderata of chemistry and economics.
  • the alkyl Grignard reagent is advantageously employed at a concentration within the range of about 1.5 to about 3.5 Normal, preferably within the range of about A2'to about 2.5 Normal at the start of electrolysis.
  • Enough high boiling ether and tetrahydrouran (which, of course, is an ether) should be used so that approximately one mol lof ether is available for each molecule of magnesium chloride formed in the. electrolysis.
  • High boiling ether may thus be employed at a concentration of from about l to about 90%, more or Y less, Vby weightof solution, while tetrahydrofuran may suitably be used at a concentration between about 2 and 60% or more by weight.
  • the aromatic hydrocarbon can vary over a broad range, with as little as 2 or 3 weight percent offering' substantial advantages which are even further increased byusing concentrations of as high as 50 weight percent or more.
  • Alkyl halide concentrations of, say, 1-50 weight percent-tof total electrolyte should also be used, since excess alkyl halide materially improves electrolyte conductivity vand reduces the formation of byproduct ga'ses.
  • the alkylGrignard reagents are chosen to produce the desired tetraalkyl lead product.
  • Alkyl lead compounds having from 1 to about 4 ycarbon atoms per alkyl group are most effectively produced by the electrolytic process.
  • mixed Grignard reagents such as a mixture of ethyl Grignard and methyl Grignard, or a mixture of ethyl Grignard with methyl halide, a mixed tetraalkyl lead compound may be'prepared; thus, dimethyl diethyl lead can be produced readily.
  • the halide portion of the alkyl Grignard reagent may be the chloride, bromide, or less, desirably, the iodide'.
  • Conditions in a typical electrolytic cell advantageously include a temperature Within the range of about 20 C. to about 100 C., preferably about 20450o C., and optimally about 25-35 C.
  • Acurrent density, at both the anode and cathode, withinV the range of about 0.2 to about 100 amperes per lsquare foot is advantageously employed.
  • Relatively low voltages, of the order of about 20-30 volts, are preferred, although cell voltages of 50 volts and even higher maybe utilized.
  • Cell pressures may range from atmospheric Vto low superatmospheric, say 60 p.s.i.g., but are preferably lower, i.e. less than about 30 p.s.i.g.
  • Theelectrolysis is advantageously continued, in either a batchwise or continuous process, until a substantial amount of the Grignard reagent is converted to tetraalkyl leadandadvantage'ously is conducted until at least a major amount, and preferably at least about 80% of the Grignard reagentV is so converted.
  • Grignard solution from preparation zone 11 is 1.98 molar with respect to methyl Grignard and has an approximate composition of 3638 parts by weight of alkyl Grignard reagent in hexylethyl ether of diethylene glycol, 1307 parts of benzene, 131 parts of tetrahydrofuran,and 103 parts ofrmethyl chloride.
  • Electrolysis is commenced and temperature is maintained at 36-41 C. by recirculation of electrolyte through an external heat exchanger, not shown. Electrolysis is commenced with an initial plate voltage of 17.5 and an amperage of 19.0, which voltage is progressively increased during the run to a maximum of 40.4 volts at the termination, l1 hours. The average voltage is 24.9, while the average temperature is 41.1 C. and pressure is 3.1 p.s.i.g.
  • Grignard conversion is 95.3%, of which 99.1% is traceable to tetramethyl lead.
  • the current eiliciency is 158% of theoreticahand the power required is 2.86 kilowatt hours per pound of tetramethyl lead.
  • the reacton mixture is withdrawn via line 27 and .conducted to subatmospheric pressure distillation towerZS.
  • This tower advantageously operating at a pressure below about 500 millimeters mercury absolute and a 'pot temperature below about C., and having, say, 5-20 theoretical plates and aV reflux ratio of about 5-20 reux-to-product, separates an overhead containing substantially all of the unreacted excess' alkyl halide; substantially all of the tetrahydrofuran, and at least a major portion of the benzene from a bottoms containing substantiallyall of the tetramethyl lead, unreacted Grignard reagent, magnesium chloride, ⁇ a minor amount of the benzene, and hexylethyl ether of diethylene glycol.
  • Tower 28 can easily be operated so that the overhead contains less'than 3% by weight of the tetramethyl lead production while the bottoms contains less than about V0.5% of the' tetrahydrofur'an.
  • the bottoms fromV tower28 contain more than 97% of the tetramethyl lead together with unreacted Grignard reagent, magnesium halide, less'than about half of the benzene, and hexylethyl ether of diethylene glycol.V This stream is transferred via line 41 to hydrolyzing tank 42, equipped with a stirrer 43 or other equivalent agitating device.
  • a stream of aqueous hydrochloric acid e.g., 3% by weight, is admitted via source 44 and line 46;
  • the amount of hydrochloric acid added is stoichiometrically equivalent to the unreacted Grignard reagent, while the amount of water is at least that necessary-to dissolve magnesium chloride formed by decomposition of the Grignard and that initially present as an etherate complex in the electrolytic reaction mixture.
  • aqueous magnesium chloride-containing phase and organic phase is pumped via line 47 to settling drum 48.
  • the heavier aqueous phase is withdrawn viapline 49 as a bottoms material, while the 'organic phase is'taken overhead via line V51.
  • The'raqueous phase contains-substantially less than a percent or so each of hexylethyl ether of diethylene glycol, benzene, and tetramethyl lead, and may be disposed of, advantageously after decomposition of the lead by chlorination.
  • distillation tower 52 is supplied with steam to effect separation of the tetramethyl lead (and benzene) from hexylethyl ether.
  • Tower 52 may have, say, 3-8 theoretical plates and may operate at a pressure not substantially above atmospheric, e.g., 15 p.s,i.a., with reboiler temperature below about 110 C. and a reux ratio of between about 1 and 5.
  • the product of the inventive process is recovered via line 62. It is composed of tetramethyl lead, together with some-usually a minor amountof benzene and a small amount of dissolved and/or entrained water. It may be dried before blending into motor or aviation mix according to well known techniques and recipes.
  • the bottoms from distillation tower 52 is composed almost entirely of the high boiling hexylethyl ether of diethylene glycol, with a small amount of water and tetramethyl lead being present. It is taken olf via line 63, sent to settling drum 64 Where the aqueous phase is removed via line 66 and the bulk of ether is transported via line 67 to drying tower 68.
  • Tower 68 having, say, 1-5 theoretical plates and a reux ratio in the range of about 1-5, and operating at a pressure of not substantially above atmospheric, e.g., 14.5 p.s.i.a. with the reboiler temperature of up to about 130 C., effectuates drying of the ether by fractional distillation.
  • Water is taken overhead via line 69 (through a conventional reux system, not shown), while the dried ether is conducted via line 71 to the electrolysis zone via Grignard prep-aration zone 11 and, optionally, via a solid desiccant 72 such as absorbent alumina or a molecular sieve.
  • a solid desiccant 72 such as absorbent alumina or a molecular sieve.
  • tower 52 may be operated under vacuum in order to maintain the reboiler temperature below the desired maximum of about 110 C.
  • a subatmospheric pressure of, say, 300 millimeters mercury absolute is imposed, and the overhead will consist of tetramethyl lead and benzene, while the bottoms will consist of hexylethyl ether of diethylene glycol with possibly a small amount of tetramethyl lead.
  • overhead receiver 58 will have only a single phase therein, and accordingly aqueous product line 61 may be dispensed with.
  • the iinal tetrarnethyl lead product is of high quality
  • a process ⁇ for recovering a tetraalkyl lead product and solvent from the electrolytic reaction mixture obtained by electrolyzing an alkyl Grignard reagent with a lead anode in a solvent comprising excess alkyl halide, a high boiling ether, tetrahydrofuran, and an aromatic hydrocarbon which process comprises: distilling said mixture to obtain an overhead containing excess alkyl halide, tetrahydrofuran, and aromatic hydrocarbon, together with a bottoms containing tetraalkyl lead product, unreacted Grignard reagent, magnesium halide, and said high boiling ether; recovering said overhead; hydrolyzing the bottoms with aqueous hydrochloric acid; separating the resulting aqueous phase containing magnesium halide from an organic phase containing tetraalkyl lead product and said high boiling ether; and distilling said organic phase to separate tetraalkyl lead product as an overhead from the high boiling ether as bottoms.

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Description

Jan. 5, 1965 J. LlNsK ETAL RECOVERY OF TETRAALKYL. LEAD FROM ELECTROLYTIC REACTION MIXTURES Filed Dec. so. 1960 United States Patent lliee 3,164,537 Patented Jan. 5, 1965 This invention relates to organornetallic compounds, and more particularly concerns an improved electrolyti process for making tetraalkyl lead compound.
Tetraalkyl lead compounds such as tetraethyl and tetramethyl lead are commercially important organometallic compounds. It has heretofore been discovered that tetraalkyl lead compounds such as these may be prepared by electrolyzing the corresponding alkyl Grignardreagent, c g., ethyl magnesium chloride, using a lead anode. By this process, alkyl groups in the lGrignard reagent are hydrocarbon is withdrawn; this is completely dry and is suitable for recycle to alkyl Grignard preparation. The bottoms from this distillation, containing tetraalkyl lead products, unreacted Grignard reagent, magnesium halide by-product, and high boiling ether, is hydrolyzed with v ether bottoms.
transferred to the anode, forming tetraalkyl lead and giving magnesium chloride as a by-product. This electrolytic process is materially superior to the conventional sodium-lead process by reason of its lower capital, raw material, and operating expenses.
It has also been discovered that the solvent used in the electrolysis controls, to a large extent, the practical success of the process. At present, a mixture of certain high boiling ethers with lower boiling tetrahydrofuran, a normally liquid aromatic hydrocarbon such as benzene, and excess alkyl halide constitute the solvent of choice. Grignard reagents in this mixture possess high electrical conductivity, which thus reduces 12R losses and makes for high overall electrical efficiency. In addition, the solvent mixture maintains its fluidity and solvent capacity for the various reactants and products during all stages of the electrolysis. Moreover, the presence of excess alkyl halide avoids undesirable gassing and provides an electrical eiciency substantially in excess of the theoretical four Faradays per mol of product.
However, by its very complexity, mixed alkyl halideether-tetrahydrofuran-aromatic solvents' present diiculties with respect to recovering thetetraalkyl lead product and the various solvent components in a form suitable for reuse. Distillation alone, for example, is not satisfactory inasmuch as the high temperatures necessary to separate tetraalykyl lead from high boiling ethers result in chemical attack of the expensive ethers by residual Grignard reagent. Prior decomposition of the Grignard reagent by hydrolysis is not always the solution since, in that case, overhead products will Abe contaminated with water. Accordingly, the major object of this invention is to provide a process for recovering tetraalkyl lead and solvent components from the aforementioned electrolytic reaction by a procedure which combines the simplicity of distillation with the solvent-conservingfeatures of hydrolysis. At the same time, Grignard attack on the ether is virtually completely prevented, and most of the solvent can be recovered in adry form suitable for recycle. t
. In accordance with the invention, tetraalkyl lead is first manufactured by now-conventional electrolytic procedures, utilizing a lead anode and a solution of alkyl Grignard reagent in a solvent comprising excess alkyl halide, a high boiling'ether, tetrahydrofuran, and an aromatic hydrocarbon. After electrolysis has proceeded to an extent where a substantial amount of alkyl Grignard reagent is converted to tetraalkyl lead, the electrolytic reaction mixture is subjected to a rst .low-temperature distillation. To avoid mechanical problems it` may be advantageous to recycle a portion of the dry, high boiling ether-to this distillation step. The distillation overhead, containing alkyl halide, tetrahydrofuran, and aromatic aqueous hydrochloric acid to decompose the Grignard.
Hydrolysis produces two liquid phases. The aqueous phase is chiefly composed of magnesium halide, while the organic phase contains tetraalkyl lead and high boiling ether, possibly with al portion of unremoved aromatic hydrocarbon.
This organic phase is then redistilled either at subatmospheric pressure or in the presence of steam to separate a tetraalkyl lead overhead from the high boiling If this distillation employs steam, the ether may be dried by redistillation and then returned to electrolysis, while if subatmospheric pressure distillation is employed the bottoms per se are suitable for recycle. The overhead from this distillation is tetraalkyl lead product, possibly containing a small amount of aromatic hydrocarbon, and may then be Withdrawn as the nal product of the inventive process.
The invention in its various aspects will be more fully described and more clearly understood from the ensuing specification, which is to be read in conjunction with the attached single drawing showing, in schematic form, a owsheet exemplifying the principles of this invention. For sake of clarity and simplicity of presentation, many auxiliaries and utilities have been omitted from the drawing, but those skilled in the art will readily perceive the need for and appreciate the location of such items as pumps, gauges, duplicate items of equipment, distillation tower auxiliaries, etc.
Before discussing the owsheet however, it is of advantage to clarify certain aspects of the electrolytic process.. Essentially, two mols of alkyl Grignard reagent, two mols of alkyl halide, and 1 of Ametallic lead are converted to 1 mol of tetraalkyl lead and two mols of byproduct magnesium dihalide, the electrolysis requires a solvent for the Grignard reagent, and this is optimally a solution of excess alkyl halide, a high boiling ether, tetrahydrofuran, and a normally liquid aromatic hydrocarbon.
The high boilingether'may be any ether boiling above the boiling point of the particular tetraalkyl lead compound being manufactured. Of the many ethers which may be used, thosewhich are dialkyl ethers of an ethylene glycol, having at least two carbon atoms in each alkyl group and notmore than two ethylene groups in the glycol portion, are preferred, since the resultant electrolyte is able to preserve its homogeneity over a wide range of concentrations and temperatures. Thus, exemplary glycol ethers are the diethyl ether of ethylene glycol, the dibutyl ether of ethylene glycol, the`diethyl ether of dethylene glycol, the dibutyl ether of diethylene glycol, and the hexylethyl ether of diethylene glycol. Ethers other than those within the foregoing preferred class may also be used, and as examples of these there may be mentioned the dimethyl ether of diethylene glycol, the dimethyl ether of triethylene glycol, and various cyclic ethers, keeping inmind that the ether should boil higher than the tetraalkyl lead product (tetramethyl lead boils at C. and tetraethyl lead boils at about 195 C withdecomposition). t t
Aromatic hydrocarbons as'components of the electrolyte may be any of the aromatics which are liquidat room temperature and which are inert to Grignard reagents under conditions of the electrolysis. Benzene and the alkyl benzenes such as toluene, the xylenes, cumene, the cymenes, etc. may be used, although it has been found that the simpler alkyl benzenes having only methyl groups offer some advantages with respect to low boiling points and high stability.
The overall electrolyte composition may be varied over wide ranges, depending upon desiderata of chemistry and economics. Y The alkyl Grignard reagent is advantageously employed at a concentration within the range of about 1.5 to about 3.5 Normal, preferably within the range of about A2'to about 2.5 Normal at the start of electrolysis. Enough high boiling ether and tetrahydrouran (which, of course, is an ether) should be used so that approximately one mol lof ether is available for each molecule of magnesium chloride formed in the. electrolysis. High boiling ether may thus be employed at a concentration of from about l to about 90%, more or Y less, Vby weightof solution, while tetrahydrofuran may suitably be used at a concentration between about 2 and 60% or more by weight. The aromatic hydrocarbon can vary over a broad range, with as little as 2 or 3 weight percent offering' substantial advantages which are even further increased byusing concentrations of as high as 50 weight percent or more. .Alkyl halide concentrations of, say, 1-50 weight percent-tof total electrolyte should also be used, since excess alkyl halide materially improves electrolyte conductivity vand reduces the formation of byproduct ga'ses. t
It appears that the optimum electrolyte composition prior to electrolysis is an alkyl Grignard concentration of about 1.5-3.5 Normal, a high boiling ether concentration of about 40-80%, about 10-40% tetrahydrofuran, abouty 30-50weight percent aromatic,"and about 1-10 weight percent excess alkyl halide. Y
The alkylGrignard reagents are chosen to produce the desired tetraalkyl lead product. For example, an ethyl Grignard'will afford tetraethyl lead, while'a methyl Grignard will yield tetramethyl lead. Alkyl lead compounds having from 1 to about 4 ycarbon atoms per alkyl group are most effectively produced by the electrolytic process. By employing mixed Grignard reagents, such as a mixture of ethyl Grignard and methyl Grignard, or a mixture of ethyl Grignard with methyl halide, a mixed tetraalkyl lead compound may be'prepared; thus, dimethyl diethyl lead can be produced readily. The halide portion of the alkyl Grignard reagent may be the chloride, bromide, or less, desirably, the iodide'. Conditions in a typical electrolytic cell advantageously include a temperature Within the range of about 20 C. to about 100 C., preferably about 20450o C., and optimally about 25-35 C. Acurrent density, at both the anode and cathode, withinV the range of about 0.2 to about 100 amperes per lsquare foot is advantageously employed. Relatively low voltages, of the order of about 20-30 volts, are preferred, although cell voltages of 50 volts and even higher maybe utilized. Cell pressures may range from atmospheric Vto low superatmospheric, say 60 p.s.i.g., but are preferably lower, i.e. less than about 30 p.s.i.g. Theelectrolysis is advantageously continued, in either a batchwise or continuous process, until a substantial amount of the Grignard reagent is converted to tetraalkyl leadandadvantage'ously is conducted until at least a major amount, and preferably at least about 80% of the Grignard reagentV is so converted.
Turning now to the drawing,'Gregnard reagent is prepared in preparation zone 11 for Ythe ultimate preparation of tetramethyl lead. Methyl chloride -is admitted from source 12 via line V13, while'magnesiumV metal chips are chargedfrorn symbolic source 14 and line 16 to the preparation zone. Recycleether, in this case hexylethyl ether of kdiethylene glycol, isrecycled via line 17, while recycle methyl` chloride and tetrahydrofuran are introduced through line 18. Make-up .solvent components, eg., benzene, .tetrahydrofuram and ether, are charged as needed through line 19. Grignard solution from preparation zone 11 is 1.98 molar with respect to methyl Grignard and has an approximate composition of 3638 parts by weight of alkyl Grignard reagent in hexylethyl ether of diethylene glycol, 1307 parts of benzene, 131 parts of tetrahydrofuran,and 103 parts ofrmethyl chloride. (An
4 additional 347 parts of methyl chlorideis added to cell 22 during the run.) It is charged via line 21 to electrolytic cell 22, which is provided with lead anodes 23 and stainless steel cathodes 24 connected to a direct current power supply 26. Electrolysis is commenced and temperature is maintained at 36-41 C. by recirculation of electrolyte through an external heat exchanger, not shown. Electrolysis is commenced with an initial plate voltage of 17.5 and an amperage of 19.0, which voltage is progressively increased during the run to a maximum of 40.4 volts at the termination, l1 hours. The average voltage is 24.9, while the average temperature is 41.1 C. and pressure is 3.1 p.s.i.g. Grignard conversion is 95.3%, of which 99.1% is traceable to tetramethyl lead. The current eiliciency is 158% of theoreticahand the power required is 2.86 kilowatt hours per pound of tetramethyl lead.
After the 11 hours of electrolysis, the reacton mixture is withdrawn via line 27 and .conducted to subatmospheric pressure distillation towerZS. This tower, advantageously operating at a pressure below about 500 millimeters mercury absolute and a 'pot temperature below about C., and having, say, 5-20 theoretical plates and aV reflux ratio of about 5-20 reux-to-product, separates an overhead containing substantially all of the unreacted excess' alkyl halide; substantially all of the tetrahydrofuran, and at least a major portion of the benzene from a bottoms containing substantiallyall of the tetramethyl lead, unreacted Grignard reagent, magnesium chloride,` a minor amount of the benzene, and hexylethyl ether of diethylene glycol. Tower 28 can easily be operated so that the overhead contains less'than 3% by weight of the tetramethyl lead production while the bottoms contains less than about V0.5% of the' tetrahydrofur'an.
In tower 28 the overhead vapors pass via vapor line 29 to condenser 31, where substantially all of the overhead components other than a portion of the methyl chloride and by-product methane gas areV condensed. From condenser 31V the condensate and Uncondensed gas pass via line 32 to overhead receiver 33, which supplies reflux to tower 28 via line 34, and recycle dry solvent to Grignard kpreparation tank 11 Vialine 36. Uncondensed material in overhead receiver 33 passes fvia vapor line 37 to refrigeration condenser 38 where methyl chloride is condensed and returned to receiver 33, while methane and other noncondensible gases are exhausted via line 39 to the atmosphere. f
The bottoms fromV tower28 contain more than 97% of the tetramethyl lead together with unreacted Grignard reagent, magnesium halide, less'than about half of the benzene, and hexylethyl ether of diethylene glycol.V This stream is transferred via line 41 to hydrolyzing tank 42, equipped with a stirrer 43 or other equivalent agitating device. Here a stream of aqueous hydrochloric acid, e.g., 3% by weight, is admitted via source 44 and line 46; The amount of hydrochloric acid added is stoichiometrically equivalent to the unreacted Grignard reagent, while the amount of water is at least that necessary-to dissolve magnesium chloride formed by decomposition of the Grignard and that initially present as an etherate complex in the electrolytic reaction mixture.
From hydrolysistank V42jthe resultant mixture of aqueous magnesium chloride-containing phase and organic phase is pumped via line 47 to settling drum 48. Here the heavier aqueous phase is withdrawn viapline 49 as a bottoms material, while the 'organic phase is'taken overhead via line V51. The'raqueous phase contains-substantially less than a percent or so each of hexylethyl ether of diethylene glycol, benzene, and tetramethyl lead, and may be disposed of, advantageously after decomposition of the lead by chlorination. ,Y The organic phase contains substantially all (except minor losses) of the tetramethyl lead, together with hexylethyl ether of diethylene glycol and aromatic hydro- 3,1 ease? carbon. It is conducted via line 51 to distillation tower In the embodiment depicted in the drawing, distillation tower 52 is supplied with steam to effect separation of the tetramethyl lead (and benzene) from hexylethyl ether. Tower 52 may have, say, 3-8 theoretical plates and may operate at a pressure not substantially above atmospheric, e.g., 15 p.s,i.a., with reboiler temperature below about 110 C. and a reux ratio of between about 1 and 5. Steam is admitted near the bottom via line 53, while the steam-tetramethyl lead-benzene overhead is passed via vapor line 54, condenser 56, and condensate line 57 to overhead receiver 58. The aqueous layer, consisting essentially of water with a small amount of dissolved benzene and tetramethyl lead, is taken from the upper portion of overhead receiver 58 and relluxed to the tower 52 via line 59, with the excess being discarded via line 61. Steam may be employed in amounts of between about 0.1 and l mols/mol feed.
The product of the inventive process is recovered via line 62. It is composed of tetramethyl lead, together with some-usually a minor amountof benzene and a small amount of dissolved and/or entrained water. It may be dried before blending into motor or aviation mix according to well known techniques and recipes.
The bottoms from distillation tower 52 is composed almost entirely of the high boiling hexylethyl ether of diethylene glycol, with a small amount of water and tetramethyl lead being present. It is taken olf via line 63, sent to settling drum 64 Where the aqueous phase is removed via line 66 and the bulk of ether is transported via line 67 to drying tower 68. Tower 68, having, say, 1-5 theoretical plates and a reux ratio in the range of about 1-5, and operating at a pressure of not substantially above atmospheric, e.g., 14.5 p.s.i.a. with the reboiler temperature of up to about 130 C., effectuates drying of the ether by fractional distillation. Water is taken overhead via line 69 (through a conventional reux system, not shown), while the dried ether is conducted via line 71 to the electrolysis zone via Grignard prep-aration zone 11 and, optionally, via a solid desiccant 72 such as absorbent alumina or a molecular sieve.
As an alternate to the use of steam, tower 52 may be operated under vacuum in order to maintain the reboiler temperature below the desired maximum of about 110 C. For this operation, a subatmospheric pressure of, say, 300 millimeters mercury absolute is imposed, and the overhead will consist of tetramethyl lead and benzene, while the bottoms will consist of hexylethyl ether of diethylene glycol with possibly a small amount of tetramethyl lead. For Vacuum operation, overhead receiver 58 will have only a single phase therein, and accordingly aqueous product line 61 may be dispensed with. Similarly, there is no need for settling drum 64, drying tower 68, or desiccant 72, since the ether is recovered in a dry form, suitable for recycle to the electrolysis, and via line 70 to the first distillation in tower 28.
The iinal tetrarnethyl lead product is of high quality,
exemplary description. It is intended to embrace all such alternatives, modifications and variations as fall within the spirit and broad scope of the appended claims.
We claim:
1. A process `for recovering a tetraalkyl lead product and solvent from the electrolytic reaction mixture obtained by electrolyzing an alkyl Grignard reagent with a lead anode in a solvent comprising excess alkyl halide, a high boiling ether, tetrahydrofuran, and an aromatic hydrocarbon, which process comprises: distilling said mixture to obtain an overhead containing excess alkyl halide, tetrahydrofuran, and aromatic hydrocarbon, together with a bottoms containing tetraalkyl lead product, unreacted Grignard reagent, magnesium halide, and said high boiling ether; recovering said overhead; hydrolyzing the bottoms with aqueous hydrochloric acid; separating the resulting aqueous phase containing magnesium halide from an organic phase containing tetraalkyl lead product and said high boiling ether; and distilling said organic phase to separate tetraalkyl lead product as an overhead from the high boiling ether as bottoms.
2. Process of claim l wherein distillation of said electrolytic reaction mixture is effected at a pressure of below about 500 millimeters mercury absolute and at a temperature of below about C.
3. Process of claim 1 wherein distillation of said organic phase is effected at subatmospheric pressure.
4. Process of claim 1 wherein distillation of said organic phase is eifected in the presence of steam, the resultant overhead is separated from water, and the resultant high boiling ether bottoms are redistilled to eiect drying thereof. y
5. Process of claim l wherein said tetraalkyl lead product is tetramethyl lead.
6. Process of claim 1 wherein said tetraalkyl lead product is tetraethyl lead.
7. A process for recovering a tetraalkyl lead product and solvent from the electrolytic reaction mixture obtained by electrolyzing the corresponding alkyl Grignard reagent with a lead anode in a solvent comprising an exfcess of the corresponding alkyl halide, a dialkyl ether of an ethylene glycol having at least two carbon atomsin each alkyl group and not more than two ethylene groups in the glycol portion, tetrahydrofuran, and an aromatic hydrocarbon, which process comprises: distilling said mixture to obtain a dry overhead containing substantially all of the unreacted excess alkyl halide and tetrahydrofuran and at least a major portion of the aromatic hydrocarbon, together with a bottoms containing substantially all of the tetraalkyl lead product, unreacted Grignard reagent, magnesium halide, a minor portion of the aromatic hydrocarbon, and ether, recovering said overhead; hydrolyzing the bottoms with suicient aqueous hydrochloric acid to dissolve the magnesium halide; separating the resulting aqueous phase containing magnesium halide from an organic phase containing tetraalkyl lead product, aromatic hydrocarbon, and ether; and distilling said organic phase to separate tetraalkyl lead and atleast a portion of the aromatic hydrocarbon as an overhead from the ether bottoms.
References Cited in the tile of this patent UNITED STATES PATENTS 2,535,190 Calingaert Dec. 26, 1950 2,777,867 Giraitis et al 1 Ian. 15, 1957 2,944,948 Giraitis et al July 12, 1960 2,985,568 Ziegler et al. May 23, 1961 3,007,858 Braithwaite Nov. 7, 1961 3,028,319 Kobetz et al Apr. 3, 1962

Claims (1)

1. A PROCESS FOR RECOVERING A TETRAALKYL LEAD PRODUCT AND SOLVENT FROM THE ELECTROLYTIC REACTION MIXTURER OBTAINED BY ELECTROLYZING AN ALKYL GRINGNARD REAGENT WITH A LEAD ANODE IN A SOLVENT COMPRISING EXCESS ALKYL HALIDE, A HIGH BOILING ETHER, TETRAHYDROFURAN, AND AN AROMATIC HYDROCARBON, WHICH PROCESS COMPRISES: DISTILLING SAID MIXTURE TO OBTAIN AN OVERHEAD CONTAINING EXCESS ALKYL HALIDE, TETRAHYDROFURAN, AND AROMATIC HYDROCARBON, TOGETHER WITH A BOTTOMS CONTAINING TETRAALKYL LEAD PRODUCT, UNREACTED GRIGNARD REAGENT, MAGNESIUM HALIDE, AND SAID HIGH BOILING ETHER; RECOVERING SAID OVERHEAD; HYDROLYZING THE BOTTONS WITH AQUEOUS HYDROCHLORIC ACID; SEPARATING THE RESULTING AQUEOUS PHASE CONTAINING MAGNESIUM HALIDE FROM AN ORGANIC PHASE CONTAINING TETRAALKYL LEAD PRODUCT AND SAID HIGH BOILING ETHER; AND DISTILLING SAID ORGANIC PHASE TO SEPARATE TETRAALKYL LEAD PRODUCT AS AN OVERHEAD FROM THE HIGH BOILING ETHER AS BOTTOMS.
US79845A 1960-03-15 1960-12-30 Recovery of tetraalkyl lead from electrolytic reaction mixtures Expired - Lifetime US3164537A (en)

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NL262356D NL262356A (en) 1960-03-15
LU39891D LU39891A1 (en) 1960-03-15
US35078A US3118825A (en) 1960-03-15 1960-06-09 Electrochemical process for the production of organometallic compounds
US35441A US3155602A (en) 1960-03-15 1960-06-13 Preparation of organic lead compounds
US67178A US3298939A (en) 1960-03-15 1960-11-04 Electrolytic preparation of organolead compounds
US79845A US3164537A (en) 1960-03-15 1960-12-30 Recovery of tetraalkyl lead from electrolytic reaction mixtures
FR855672A FR1287026A (en) 1960-03-15 1961-03-15 Improvements in processes for the preparation of tetraalkylated lead compounds
GB9445/61A GB984421A (en) 1960-03-15 1961-03-15 Electrolytic production of lead alkyl compounds
DEST17583A DE1157616B (en) 1960-03-15 1961-03-15 Process for the production of tetraalkyl lead
US547780A US3584050A (en) 1960-03-15 1966-05-05 Nitrated aromatic alkamines
SE6606793A SE375521B (en) 1960-03-15 1966-05-17
SE7011413A SE379040B (en) 1960-03-15 1966-05-17
IL25803A IL25803A (en) 1960-03-15 1966-05-17 Antimicrobial compositions containing nitrated alkamines and new nitrated alkamines
GB22126/66A GB1142337A (en) 1960-03-15 1966-05-18 Amino nitroalkanes and their use as microbiocides
NO163070A NO115641B (en) 1960-03-15 1966-05-18
IT11441/66A IT986753B (en) 1960-03-15 1966-05-20 PROCEDURE FOR THE PRODUCTION OF USEFUL AMINO NITROALKANES SUCH AS INSECTICIDES AND SIMILAR FUNGICIDES AND PRODUCT OBTAINED
NL6606997.A NL159975C (en) 1960-03-15 1966-05-20 METHOD FOR PREPARING SECONDARY OR TERTIARY N- (2-NITROALKYL) AMINES ACTIVE AGAINST HARMFUL ORGANISMS; PROCESS FOR PREPARING PREPARATIONS ACTIVE AGAINST HARMFUL ORGANISMS; THE MOLDED PRODUCTS THEREFORE OBTAINED, AND PROCEDURE FOR CONTROLLING MICROORGANISMS THAT CAUSE SLUMMATION AND DEGRADATION IN PAPER MANUFACTURE.
FR62411A FR1494137A (en) 1960-03-15 1966-05-20 Antimicrobial and pesticide compounds and compositions, their manufacturing processes and applications in agriculture and industry
BE681371D BE681371A (en) 1960-03-15 1966-05-20
AT1227268A AT314092B (en) 1960-03-15 1966-05-20 Process for the inhibition of the growth of lower animals or plants and means for its implementation
AT481966A AT288340B (en) 1960-03-15 1966-05-20 Process for the preparation of aminonitroalkanes
FI661331A FI51171C (en) 1960-03-15 1966-05-20 Aminonitroalkanes for use as antimicrobial agents.
BR179699/66A BR6679699D0 (en) 1960-03-15 1966-05-20 PROCESS FOR THE PREPARATION OF AMINO-MITROALKANS AND PESTICIDAL COMPOSITES BASED ON THE SAME
DK258666AA DK125262B (en) 1960-03-15 1966-05-20 Bactericides, fungicides, nematocides and algicides.
DE1620004A DE1620004C3 (en) 1960-03-15 1966-05-20 Pesticides containing N-0-phenyl-2-nitropropyi) -piperacias, their metal salts and such compounds
CH119169A CH534121A (en) 1960-03-15 1966-05-23 Process for the preparation of compounds substituted with an amino group on the B-C atom and with a nitro group on the a-C atom
CH119269A CH505551A (en) 1960-03-15 1966-05-23 Pesticides
CH739566A CH490318A (en) 1960-03-15 1966-05-23 Process for the preparation of compounds substituted with an amino group on the B carbon atom and with a nitro group on the a carbon atom

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US1521160A 1960-03-15 1960-03-15
US35078A US3118825A (en) 1960-03-15 1960-06-09 Electrochemical process for the production of organometallic compounds
US3544060A 1960-06-13 1960-06-13
US35441A US3155602A (en) 1960-03-15 1960-06-13 Preparation of organic lead compounds
US67178A US3298939A (en) 1960-03-15 1960-11-04 Electrolytic preparation of organolead compounds
US79845A US3164537A (en) 1960-03-15 1960-12-30 Recovery of tetraalkyl lead from electrolytic reaction mixtures
US8526761A 1961-01-27 1961-01-27
US457802A US3399199A (en) 1965-05-21 1965-05-21 Nitroalkyl-piperazines
US54778066A 1966-05-05 1966-05-05

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US35441A Expired - Lifetime US3155602A (en) 1960-03-15 1960-06-13 Preparation of organic lead compounds
US67178A Expired - Lifetime US3298939A (en) 1960-03-15 1960-11-04 Electrolytic preparation of organolead compounds
US79845A Expired - Lifetime US3164537A (en) 1960-03-15 1960-12-30 Recovery of tetraalkyl lead from electrolytic reaction mixtures
US547780A Expired - Lifetime US3584050A (en) 1960-03-15 1966-05-05 Nitrated aromatic alkamines

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DE (2) DE1157616B (en)
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3312605A (en) * 1961-02-13 1967-04-04 Nalco Chemical Co Preparation of organo metallic compounds
US3359291A (en) * 1964-10-05 1967-12-19 Nalco Chemical Co Purification of tetraalkyl lead
US3380900A (en) * 1964-11-05 1968-04-30 Nalco Chemical Co Electrolytic preparation of organic lead compounds and electrolyte therefor
US3393137A (en) * 1965-12-14 1968-07-16 Nalco Chemical Co Solvent recovery process
US3403983A (en) * 1965-01-11 1968-10-01 Mallinckrodt Chemical Works Steam distillation of metal values in solution
US3408273A (en) * 1964-03-11 1968-10-29 Nalco Chemical Co Organic lead recovery from electrolytes by steam and azeotropic distillation
US3409518A (en) * 1966-01-06 1968-11-05 Nalco Chemical Co Organic halide recovery
US3450608A (en) * 1966-03-09 1969-06-17 Nalco Chemical Co Purification of ethers

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3256161A (en) * 1961-02-13 1966-06-14 Nalco Chemical Co Manufacture of tetramethyl lead
DE1250441B (en) * 1964-05-11 1967-09-21 Ethyl Corporation, Baton Rouge, La. (V. St. A.) Process for the production of alkyl vinyl lead compounds
US3380899A (en) * 1964-10-16 1968-04-30 Nalco Chemical Co Electrolytic preparation and recovery of tetraalkyl lead compounds
US3522156A (en) * 1964-10-21 1970-07-28 Ethyl Corp Production of hydrocarbon lead compounds
US3372098A (en) * 1965-01-21 1968-03-05 Nalco Chemical Co Process for recovering solvents from electrolytes
US3458410A (en) * 1965-07-30 1969-07-29 Nalco Chemical Co Purification of ethers
AU4220689A (en) * 1988-09-06 1990-04-02 Lubrizol Corporation, The Nitro-groups containing amines, and fuels compositions containing same
US9145341B2 (en) * 2012-11-19 2015-09-29 Technion Research & Development Foundation Limited Process of preparing Grignard reagent

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2535190A (en) * 1949-04-01 1950-12-26 Ethyl Corp Manufacture of alkyllead compounds
US2777867A (en) * 1953-08-03 1957-01-15 Ethyl Corp Recovery of alkyllead compounds
US2944948A (en) * 1956-02-06 1960-07-12 Ethyl Corp Method of purifying organometallic complexes and their use in the preparation of organolead compounds
US2985568A (en) * 1954-11-26 1961-05-23 Ziegler Electrolytic process for the production of metal alkyls
US3007858A (en) * 1959-05-06 1961-11-07 Nalco Chemical Co Preparation of organo metallic compounds
US3028319A (en) * 1960-02-01 1962-04-03 Ethyl Corp Manufacture of magnesium organo compounds

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE569921A (en) * 1957-07-31
US2960450A (en) * 1959-10-16 1960-11-15 Ethyl Corp Organo manganese compounds

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2535190A (en) * 1949-04-01 1950-12-26 Ethyl Corp Manufacture of alkyllead compounds
US2777867A (en) * 1953-08-03 1957-01-15 Ethyl Corp Recovery of alkyllead compounds
US2985568A (en) * 1954-11-26 1961-05-23 Ziegler Electrolytic process for the production of metal alkyls
US2944948A (en) * 1956-02-06 1960-07-12 Ethyl Corp Method of purifying organometallic complexes and their use in the preparation of organolead compounds
US3007858A (en) * 1959-05-06 1961-11-07 Nalco Chemical Co Preparation of organo metallic compounds
US3028319A (en) * 1960-02-01 1962-04-03 Ethyl Corp Manufacture of magnesium organo compounds

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3312605A (en) * 1961-02-13 1967-04-04 Nalco Chemical Co Preparation of organo metallic compounds
US3408273A (en) * 1964-03-11 1968-10-29 Nalco Chemical Co Organic lead recovery from electrolytes by steam and azeotropic distillation
US3359291A (en) * 1964-10-05 1967-12-19 Nalco Chemical Co Purification of tetraalkyl lead
US3380900A (en) * 1964-11-05 1968-04-30 Nalco Chemical Co Electrolytic preparation of organic lead compounds and electrolyte therefor
US3403983A (en) * 1965-01-11 1968-10-01 Mallinckrodt Chemical Works Steam distillation of metal values in solution
US3393137A (en) * 1965-12-14 1968-07-16 Nalco Chemical Co Solvent recovery process
US3409518A (en) * 1966-01-06 1968-11-05 Nalco Chemical Co Organic halide recovery
US3450608A (en) * 1966-03-09 1969-06-17 Nalco Chemical Co Purification of ethers

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CH534121A (en) 1973-02-28
CH505551A (en) 1971-04-15
IT986753B (en) 1975-01-30
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AT314092B (en) 1974-03-25
GB984421A (en) 1965-02-24
US3584050A (en) 1971-06-08
AT288340B (en) 1971-02-25
NL6606997A (en) 1966-11-22
SE375521B (en) 1975-04-21
SE379040B (en) 1975-09-22
DK125262B (en) 1973-01-29
US3155602A (en) 1964-11-03
DE1620004A1 (en) 1970-02-12
FI51171B (en) 1976-08-02
DE1620004B2 (en) 1978-09-14
DE1620004C3 (en) 1979-05-10
GB1142337A (en) 1969-02-05
BE681371A (en) 1966-11-21
NL262356A (en)
BR6679699D0 (en) 1973-04-12
US3298939A (en) 1967-01-17
LU39891A1 (en)
DE1157616B (en) 1963-11-21
NL159975B (en) 1979-04-17
FI51171C (en) 1976-11-10
IL25803A (en) 1971-05-26
NL159975C (en) 1979-09-17
US3118825A (en) 1964-01-21

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