US3739027A - Hydrogenation of nitroparaffins - Google Patents

Hydrogenation of nitroparaffins Download PDF

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Publication number
US3739027A
US3739027A US00145873A US3739027DA US3739027A US 3739027 A US3739027 A US 3739027A US 00145873 A US00145873 A US 00145873A US 3739027D A US3739027D A US 3739027DA US 3739027 A US3739027 A US 3739027A
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temperature
weight percent
bed
conversion
reactor
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US00145873A
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W Gates
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Texaco Inc
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Texaco Inc
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M3/00—Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/26—Amines

Definitions

  • This invention relates to the production of amines and more particularly to the production of secondary alkyl primary amines having from 6 to 25 carbon atoms from secondary mono-nitroparafiins.
  • Another object of this invention is to provide a process for selectively converting mono-nitroparafl'ins to secondary alkyl primary amines in high yields.
  • this invention contemplates a process for the catalytic hydrogenation of a secondary mono-nitroparaffin wherein hydrogen and nitroparaflin flow through a hydrogenation catalyst bed under conditions effective to convert said nitroparaflin to a secondary alkyl primary amine, the improvement which comprises passing said nitroparaflin through said catalyst bed at an average conversion temperature of from 200 to 450 F. and maintaining a difference of at least 100 F. between the maximum conversion temperature in said bed and inlet temperature of said bed.
  • the difference (AT) between the maximum conversion temperature and the conversion temperautre at the inlet is at least 100 F. and up to 400 F. and preferably AT is from 150 to 300 F.
  • This difference, AT is effectively maintained by operating at inlet temperatures of from 100 to 400 F., preferably 150 to 250 F. and up to a maximum conversion temperature of 500 F. Temperatures above 500 F. adversely affect the process in that nitrogen is lost most probably as NH from the cracking off of the amine group.
  • the inlet temeprature contemplated is, for example, 100 F. a AT of at least 200 F. is employed so as to provide an average conversion temperature of 200 F.
  • the designated inlet temperature is attained by introducing the nitroparaflin feed at a temperature of from 100 to 400 F.
  • the instant invention contemplates a continuous process for producing secondary alkyl primary amines by reacting mono-nitroparaffins having from 6 to 25 carbon atoms with hydrogen.
  • Mono-nitroparaflins encompassed within this process constitute secondary nirtro-nparafiins in which the nitro group is randomly positioned along the carbon chain on other than a terminal carbon atom.
  • Such mono-nitroparaffins are provided by contacting a C C paraflin hydrocarbon, preferably a straight chain hydrocarbon, in a liquid phase with a vaporous nitrating agent illustrated by nitrogen dioxide or nitric acid at a temperature ranging from about 250 to 500 F. and pressures of from 1 to 20 atmospheres.
  • the illustrative nitration reaction briefly outlined above is generally permitted to proceed until about 5 to 50 percent of the paraffin has. been converted yielding a crude nitrated product of about 5 to 45 percent of mononitroparaffin and to 50 percent of unreacted paraffin along with lesser amounts of C C ketone, alcohol, carboxylic acid and polyfunctionals.
  • nitration to 10 to 25 weight percent nitroparaflin is undertaken.
  • the mononitroparafiin so prepared may if desired be separated and recovered from the crude product as by distillation and subsequently hydrogenated to the corresponding amine, the reaction conveniently undertaken in the presence of a C -C parafiin hydrocarbon diluent.
  • crude material comprising up to about 25 weight percent nitroparafiin may be hydrogenated directly wherein the unreacted paraffin constitutes the reaction medium.
  • the crude nitrated product may also be caustic washed with for example sodium bicarbonate, ammonium hydroxide, sodium hydroxide or potassium hydroxide to remove acid by-products following nitration and prior to hydrogenation.
  • the nitroparafiin feedstock is provided substantially free of acid by-products or contaminants neutralization may be omitted. Irrespective of whether caustic treatment is provided the feed introduced to the catalyst bed comprises from about 5 to 25 weight percent nitroparalfin in a C -C paraffin hydrocarbon diluent.
  • the nitroparaffin stream is introduced at an inlet temperature of from 100 to 400 F. to a bed of hydrogenation catalyst along with hydrogen under conditions such that at least 80 weight percent and preferably at least 90 weight percent of the nitroparafiin is selectively converted to at least 90 weight percent primary amine.
  • Conversion conditions in the reactor containing the hydrogenation catalyst in addition to the reactor inlet temperature, maximum temperature and AT include liquid hourly space velocities of from 0.5 to 20 liquid volumes of nitroparaffin per volume of catalyst per hour and particularly space velocities of from 1.0 to 4.0 v./ v./ hr.
  • the selectivity of the process to primary amine is dependent upon the relationship between the average conversion temperature, AT and the space velocity heretofore recited.
  • the amine may first be converted and recovered as an amine salt by reaction with an inorganic acid followed by further treatment of the amine salt with alkali and thereafter recovering the primary amine by distillation.
  • Amines produced according to this process may be employed as mold release agents, emulsion freeze-thaw stabilizers, pigment dispersing agents, polyurethan catalysts and anticaking anti-dusting agents. Their uses are also indicated as corrosion inhibitors, deleterious bacteria control agents, sludge dispersants and as detergents and de-icers in gasolines.
  • Example I In the following experiments a hydrogenation reactor having an inside diameter of 1 inch was loaded with 61 grams of a conventional and commercially available nickel catalyst forming a bed 8 inches deep.
  • a C -C feedstock composed of 14.5 weight percent mono-nitroparaffin, 82 weight percent n-paraffin, 1.5 weight percent ketone and 2 weight percent alcohols, nitrites, nitrates and difunctional paraffin saturated with ammonia at 50 to 75 p.s.i.g. was introduced at the rate of 67 grams per hour into the above reactor to effect the reduction of the nitroparaflin in the feedstock to the corresponding amine.
  • Hydrogen at a pressure of from 550-600 p.s.i.g.
  • the feedstock was introduced to the reactor at an inlet temperature of 220 F., the maximum temperature of bed was 390 F., the average temperature being 305 F. and a AT of 170 F.
  • the efiluent from the reactor contained 10.3 mg. NH /g. and 0.26 mg. NH/g. thus indicating that 93 percent of the nitroparafiin have been converted to amines with a selectivity to secondary alkyl primary amine of percent.
  • the beneficial effect of a AT of F. provided high selectivity and high conversion of mono-nitroparafiin to secondary alkyl primary amine.
  • Example III A hydrogenation reactor having an inside diameter of about 2 /2 inches was loaded with 755 grams of the catalyst employed in Example II to form a bed 30 inches deep.
  • a C -C feedstock composed of 14.1 weight percent nitroparaffin, 82 Weight percent n-parafiin, 1.5
  • Example HI Comparing Example HI with Example II the beneficiaal effect of maintaining at AT of at least 100 F., and in the instance 170 F. is shown.
  • Example IV A hydrogenation reactor having an inside diameter of about 2 /2 inches was loaded with 676 grams (1700 cc.) of a catalyst composed of 1 weight percent palladium on carbon to form a bed 18 inches deep.
  • a C -C feedstock composed of about 14.2 weight percent nitroparaffin in about 83 weight percent n-parafiin was introduced to the reactor at a liquid hourly space velocity of 1.5 along with 9.1 cubic feet per hour of hydrogen at a hydrogen pressure of from 550-600 p.s.i.g.
  • E through I the inlet temperature, maximum temperature, average temperature and AT were varied. Table II summarizes the results.
  • Example V A hydrogenation reactor having an inside diameter of about 2 /2 inches was loaded with 680 grams (1580 cc.) of a catalyst composed of 1 weight percent palladium on carbon to form a bed 19 inches deep.
  • a feedstock composed of 12.7 weight percent C -C nitroparaflin, 83.8 weight percent C -C n-parafiin along with lesser amounts of ketones, alcohols, nitriles, nitrates and difunctional paraffin was introduced at the rate of 1770 grams per hour into the reactor corresponding to a liquid hour- 1y space velocity of 1.3.
  • the reactor inlet temperature was 280 F. and the maximum temperature within the bed was recorded at 400 F.
  • Example VI The hydrogenation reactor of the previous example was loaded with 1022 grams of a 1 percent palladium on carbon catalyst to form a bed 28 inches deep.
  • the C -C nitroparaflin feedstock of Example V was introduced to the reactor at an inlet temperature of 235 F. and at a liquid hourly space velocity of 1.4.
  • the maximum temperature within the bed was 404 F. corresponding to a AT of 169 F. and an average temperature of about 320 F.
  • Hydrogen was introduced at the rate of 10-12 cubic feet per hour at a pressure of 550-600 p.s.i.g.
  • the organic efiiuent from the reactor contained 10.4 mg. NH /g. and less than 0.4 mg. NH/g. thus indicating that percent of the nitroparaffin had been converted to amines with a selectivity to secondary alkyl primary amine of greater than 96 percent.
  • nitroparaflin comprises a mixture of C C nitroparafiins.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
US00145873A 1971-05-21 1971-05-21 Hydrogenation of nitroparaffins Expired - Lifetime US3739027A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US14587371A 1971-05-21 1971-05-21

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US3739027A true US3739027A (en) 1973-06-12

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US00145873A Expired - Lifetime US3739027A (en) 1971-05-21 1971-05-21 Hydrogenation of nitroparaffins

Country Status (11)

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US (1) US3739027A (fr)
JP (1) JPS5623977B1 (fr)
BE (1) BE780958A (fr)
BR (1) BR7202116D0 (fr)
CA (1) CA995253A (fr)
DE (1) DE2220866A1 (fr)
ES (1) ES402706A1 (fr)
FR (1) FR2131464A5 (fr)
GB (1) GB1328186A (fr)
IT (1) IT955607B (fr)
NL (1) NL7202964A (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4066699A (en) * 1976-12-27 1978-01-03 Texaco Inc. Process for the hydrogenation of nitrated paraffins using a palladium on carbon catalyst characterized by a low ash and a low halide content
US4067905A (en) * 1975-02-04 1978-01-10 Societe Chimique De La Grande Paroisse, Azote Et Produits Chimiques Preparation of 2-amino-n-butanol
US4924029A (en) * 1988-06-24 1990-05-08 W. R. Grace & Co.-Conn. Reduction of nitroaliphatics via homogeneous catalysis
US20030078344A1 (en) * 2001-10-23 2003-04-24 Huntsman Petrochemical Corporation Advances in amination

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL178963C (nl) * 1972-04-22 1986-06-16 Sumitomo Chemical Co Werkwijze ter bereiding van aniline door hydrogenering van nitrobenzeen.

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4067905A (en) * 1975-02-04 1978-01-10 Societe Chimique De La Grande Paroisse, Azote Et Produits Chimiques Preparation of 2-amino-n-butanol
US4066699A (en) * 1976-12-27 1978-01-03 Texaco Inc. Process for the hydrogenation of nitrated paraffins using a palladium on carbon catalyst characterized by a low ash and a low halide content
US4924029A (en) * 1988-06-24 1990-05-08 W. R. Grace & Co.-Conn. Reduction of nitroaliphatics via homogeneous catalysis
US20030078344A1 (en) * 2001-10-23 2003-04-24 Huntsman Petrochemical Corporation Advances in amination
US6888030B2 (en) * 2001-10-23 2005-05-03 Huntsman Petrochemical Corporation Advances in amination

Also Published As

Publication number Publication date
GB1328186A (en) 1973-08-30
BE780958A (fr) 1972-09-20
CA995253A (en) 1976-08-17
FR2131464A5 (fr) 1972-11-10
NL7202964A (fr) 1972-11-23
ES402706A1 (es) 1975-04-01
BR7202116D0 (pt) 1973-06-14
DE2220866A1 (de) 1972-12-07
IT955607B (it) 1973-09-29
JPS5623977B1 (fr) 1981-06-03

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