Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C7/00—Purification; Separation; Use of additives
  • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
  • C07C7/152—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by forming adducts or complexes
  • C07C7/156—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by forming adducts or complexes with solutions of copper salts
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S585/00—Chemistry of hydrocarbon compounds
  • Y10S585/949—Miscellaneous considerations
  • Y10S585/952—Reaction stopping or retarding

Definitions

• the rate of alkylation in the above-described systems can be substantially reduced by adding to the c'omplexing solutions, in effective amounts, phosphine materials in combination with organic nitrogen base compounds. It is believed that the alkylation rates may be reduced in the above manner because of the neutralization of the proton donor material, which is typically l-lCl, and that such neutralization by the organic, nitrogen'bases can occur even in the presence of the Lewis acid moieties such as AlCl,, BF, and the like.
• phosphine material is believed to add stability to the overall system and allow this neutralization to occur and thereby provide long range stability for the system at a better level than the organic nitrogen additive ent invention
• moieties such as trialkyl phosphines, alkylaryl phosphines, aralkyl phosphines, benzyl phosphines and materials having the general formula R,R,R,P wherein R R, and R, are monovalent radicals independently selected from the group consisting of alkyl radicals having from one to 20 carbon atoms, preferably from two to 10 carbon atoms; phenyl radicals, alkylaryl radicals having from seven to 12 carbon atoms; preferably from seven to l0 carbon atoms; aralkyl radicals having from seven to 12 carbon atoms, preferably from from seven to 10 carbon atoms.
• useful phosphine materials include triphenyl phosphine, trioctyl phosphine, tribenzyl phosphine and tritolyl phosphine.
• organic nitrogen bases useful in the present invention are generally defined as aprotic and lack other polar functional groups, they include classes of compounds known as substituted pyridines, tertiary alkyl amines, and tertiary alkylaryl amines.
• substituted pyridines is meant any alkylated pyridine having the general formula:
• a -A are monovalent radicals independently selected from the group consisting of hydrogen radicals and alkyl groups whose total number of carbon atoms ranges from-one to 18.
• the termsubstituted pyridine includes moieties such as 2, 4-, 6-trimethyl pyridine, 2,6-ditertiary butyl pyridine, 2-methyl pyridine and the like.
• tertiary alkyl amines compounds havingthe general formula, RR'R"N wherein R, R' and R" are independently selected from the group consistingtof alkyl radicals having from one to 10 carbon atoms,-preferably from one-to five carbon atoms and having at least six carbon atoms per nitrogen;
• tertiary alkylaryl amines are materials represented by the generalformula ArRR'N wherein Ar is a substituted aryl group having at least six carbon atoms and R and R have the above designated meanings.
• minor amounts is meant from 0.1 to 15 percent, preferably from 0.5 to 10 percent based on-the number of moles of the complexing salt employed. Minor amounts of these additives are used to avoid excessive loss of complexing capacity of thecomplexing salt and moreoversince minor amounts of said additives provide sufficient stability bylowering alkylation side reactions to a minimum. 1 I
• the complexing solution may be generally described as low volatility aromatic solvents-containing cuprous or silver complexing salts such as CuPF CuBR, CuBF,Cl,.CuAlCl -CuAlBr CuTaF. and CuAlCl,Br, where x y 4.
• aromatic solvents-containing cuprous or silver complexing salts such as CuPF CuBR, CuBF,Cl,.CuAlCl -CuAlBr CuTaF. and CuAlCl,Br, where x y 4.
• temperatures and pressures at which the present invention is operable are not critical and generally will range from about 20 to 300C., preferably from 50 to 140C., and from 0.01 to 0.5 atmospheres to about to 50 atmosphere pressure.
• EXAMPLE I 55.0g of a CuAlCl -methylbiphenyl-complex, 1.10g CuCl, 0.72g triphenylphosphine and 0.53 g 2,6-di-tert.- butylpyridine are heated to 140C. under a nitrogen atmosphere in a reaction vessel equipped with magnetic stirrer, gas inlet and outlet. The input and output of gas are monitored by means of two gas meters. Ethylene is introduced through a tube ending shortly above the liquid level and a slow purge of gas is maintained to avoid vapor locking. After the initial uptake of ethylene due to complexing by the copper salt is complete, no further consumption of gas can be observed over a period of 4% hours.
• Examples Ila an d llb clearly show that the combination of an organic phosphine and an organic nitrogen base is superior in terms of the duration of an olefin EXAMPLE III
• the rate of alkylation was measured by saturating the complex with ethylene at atmospheric pressure and maintaining it under an ethylene atmosphere in a thermostated glass vessel connected to an oil-fitted wet-test meter, in such a way that any ethylene uptake following the initial saturation would be recorded in the meter.
• the alkylation rate was expressed as millimoles of ethylene per mole of CuAlCl, per hour.
• EXAMPLE V In this example the solubility of pyridine AlCl complex is compared to that of collidine AlCl in benzene solutions. To separate CuAlCh-benzene solutions was added sufficient amounts of pyridine and collidine respectively. The precipitates formed were ana' lyzed for Cu, Al, Cl and C; the results of these analyzes are found below:
• An improved process for the separation and recovery of complexible olefins from olefin-containing feedstreams by contacting said feedstreams with an aromatic sorbent solution containing cuprous salts whose anionic components are Lewis acids wherein the improvement comprises incorporating into said aromatic sorbent solution a minor amount of an organic phosphine in combination with an organic nitrogen base material selected from the group comprising alkyl amines, tertiary alkylaryl amines and substituted pyridines, to thereby substantially reduce alkylation and polymerization side reactions and stabilize said aromatic sorbent solution.
• organic phosphine has the general formula R,R,R,P wherein R R,, and R are monovalent radicals independently selected from the group consisting of alkyl radicals having from one to carbon atoms, phenyl radicals, alkylaryl radicals having from seven to 12 carbon atoms and aralkyl radicals having from seven to l2 carbon atoms.
• organic nitrogen base material is an alkyl amine having the general phenylphosphine
• R, R, and R" are independently selected from the group consisting of alkyl radicals having from one to 10 carbon atoms.
• organicnitrogen base material is a substituted pyridine having the general formula:
• a A are monovalent radicals independently selected from the group consisting of hydrogen radicals and alkyl groups whose total number of carbon atoms ranges from one to 18.
• said organic nitrogen base material is a tertiary alkylaryl amine having the general formula ArRRN wherein Ar is a substituted aryl group having at least six carbon atoms; R, and R are independently selected from the group consisting of alkyl radicals having from one to 10 carbon atoms.
• cuprous salt is one selected from the group consisting of CuPF CuBF CuBF,,Cl, CuAlCl CuAlBr CuTaF, and CuAlCl,Br,, wherein x y are integers whose sum equals 4.
• organic nitrogen base is one selected from the group consisting of 2,4,6-trimethyl pyridine, 2,6-ditertiary butyl pyridine, 2,6-diethyl N,N-diethyl amine.
• organic phosphine is one selected from the group consisting of tritrioctylphosphine, tribenzylphosphine and t'ritolylphosphine.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Analytical Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Water Supply & Treatment (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Pyridine Compounds (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=22984045

Family Applications (1)

Country Status (6)

Cited By (2)

Families Citing this family (1)

Citations (5)

• 1972
  • 1972-06-02 US US00259219A patent/US3758607A/en not_active Expired - Lifetime
• 1973
  • 1973-05-30 DE DE2327599A patent/DE2327599C2/de not_active Expired
  • 1973-05-31 GB GB2602473A patent/GB1420446A/en not_active Expired
  • 1973-06-01 CA CA173,005A patent/CA999605A/en not_active Expired
  • 1973-06-01 FR FR7320105A patent/FR2186453B1/fr not_active Expired
  • 1973-06-01 JP JP6176373A patent/JPS5715565B2/ja not_active Expired

Patent Citations (5)

Also Published As

Similar Documents