US3349134A - Tar removal in phenol process - Google Patents

Tar removal in phenol process Download PDF

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Publication number
US3349134A
US3349134A US214209A US21420962A US3349134A US 3349134 A US3349134 A US 3349134A US 214209 A US214209 A US 214209A US 21420962 A US21420962 A US 21420962A US 3349134 A US3349134 A US 3349134A
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US
United States
Prior art keywords
acid
cupric
product
tarry
carboxylic acid
Prior art date
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Expired - Lifetime
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US214209A
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English (en)
Inventor
Blom Leendert
Johannes L F M Zwinkels
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Stamicarbon BV
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Stamicarbon BV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
    • C07C37/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by replacing a carboxyl or aldehyde group by a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
    • C07C39/04—Phenol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment

Definitions

  • the present invention relates to the preparation of phenols from monocarboxylic acids of the benzene series or from the salts, esters or anhydrides of such acids.
  • phenols can be prepared by pyrolytic oxidation .and decarboxylation in the liquid phase of monocarboxylic acids of the benzene series or of the salts, esters or anhydrides of such acid, in the presence of a copper compound and at a temperature at which the compound is present in the dissolved state. This reaction is carried out with the aid of molecular oxygen in the presence of water vapor, e.g., steam.
  • At least part of the copper compound used as the catalyst in this reaction consists of the copper salt of the treated carboxylic acid of the benzene series.
  • This copper salt can either be preformed or else it can be formed in the reaction zone by introducing another copper compound, e.g., cupric salicylate, cupric oxide, cuprous oxide or even metallic copper.
  • the reaction can be carried out by introducing molecular oxygen, e.g., in the form of air, and steam into the molten carboxylic acid of the benzene series or the salt, ester or anhydride thereof.
  • molecular oxygen e.g., in the form of air
  • steam into the molten carboxylic acid of the benzene series or the salt, ester or anhydride thereof.
  • the carboxylic acid or derivative thereof can be dissolved in an inert solvent, such as water.
  • the copper salt is dissolved in the liquefied carboxylic acid prior to dissolving the latter in water.
  • Air and steam are also introduced into the solution of the carboxylic acid in inert solvent.
  • this reaction yields, as a by-product, a tarry, highly viscous product which, during the reaction, remains in solution in the liquid carboxylic acid or derivative.
  • this tarry by-product must be removed from the reaction mixture and the carboxylic acid must be extracted.
  • Another object is to separate the tarry by-product from the unreacted carboxylic acid or derivative in such a process.
  • the tarry 'by-product formed is separated olf, as indicated, with an aromatic hydrocarbon, or substituted aromatic hydrocarbon containing a condensed unsaturated hydrocarbon ring.
  • the catalyst there can be used copper or any of the copper compounds set forth below, e.g., cupric benzoate, cupric o-toluate, cupric m-toluate, cupric m-nitrobenzoate, cupric p-toluate, cupric p-nitrobenzoic acid,
  • cupric p-chlorobenzoic acid cupric p-methyoxybenzoic acid, cupric p-phenylbenzoic acid, cupric 2,4-dimethyl benzoic acid, cupric salicylate, cupric oxide, cuprous oxide, metallic copper, cupric chloride, cuprous chloride, cupric sulfate, cupric nitrate.
  • salts, esters and anhydrides there can be used salts, esters and anhydrides, as previously indicated.
  • Illustrative of such starting materials are magnesium benzoate, sodium benzoate, calcium benzoate, potassium benzoate, barium benzoate, methyl benzoate, ethyl benzoate, magnesium o-toluate, propyl p-toluate, sodium m-nitrobenzoate, methyl p-nitrobenzoate, benzoic anhydride, toluic anhydride, m-nitrobenzoic anhydride, ethyl p-methoxybenzoate, p-phenylbenzoic anhydride, ethyl 2,4-dimethylbenzoate.
  • aromatic hydrocarbons and derivatives thereof containing a condensed unsaturated hydrocarbon ring system which can be used to separate off the tarry by-product, include aromatic hydrocarbons (including alkyl and other hydrocarbon substituted aromatic hydrocarbons), naphthalene, anthracene, phenanthrene, fiuorene, pyrene, a-methyl naphthalene, B-rnethyl naphthalene, dimethyl naphthalene, methyl anthracene, acenaphthene, fluoranthene, chrysene, carboxylic acids, .such as a-naphthoic acid, fi-naphthoic acid and anthracene carboxylic acid, chloro derivatives, such as u-chloronaphthalene, fl-chloronaphthalene, ot-bromonaphthalene, and dichloronaphthalene, phenols, e.
  • aromatic oils predominating in aromatic hydrocarbons containing a condensed unsaturated hydrocarbon ring system including coal tar oils, such as anthracene oil and creosote oil and high-boiling aromatic hydrocarbon residues obtained in the refining of mineral oil, and preferably boiling above 200 C.
  • the tarry by-product can be mixed with the condensed ring aromatic hydrocarbon after the phenol produced has been separated from the product of the reaction between.
  • the tarry by-product is thus converted to th form of a thin liquid which can be subjectedto an extraction with a solvent in which the carboxylic acid can be dissolved.
  • the preferred solvent for the purpose of recovering the carboxylic acid from the tar is water.
  • solvents such as alcohols, e.g.,-methanol, ethanol, isopropanol, butanol, hexanol, isooctanol and cyclohexanol, aliphatic hydrocarbons, such as hexane, heptane, decane and cyclohexane, aromatic hydrocarbons, such as benzene, toluene, xylene, bipheuyl, mesitylene, cymene and cumene, substituted hydrocarbons, e.g., ethers, such as diphenyl oxideand halohydrocarbons, such as chlorobenzene, bromobenzene, trichloroethylene, tetrachloroethylene, ,dichloroethylene, ethylene dichloride, acetylene tetrachloride and carbon tetrachloride.
  • alcohols e.g.,-methanol, ethanol, iso
  • the amount of aromatic hydrocarbon or derivative containing a condensed unsaturated hydrocarbon ring system can be varied within wide limits.
  • the amount is generally smaller in the case of nonsubstituted higher aromatic hydrocarbons than in the case of alkyl or other substituted aromatics, such as dimethylnaphthalene.
  • the amount of the aromatic hydrocarbon or derivative need not exceed 300% by Weight of the tarry by-product.
  • 35% to 100% of the aromatic hydrocarbon or derivative is used, based on the weight of the tar- If smaller amounts of the condensed ring extractant are used, the tar becomes more flowable, but nevertheless retains such a high viscosity that consider-able energy is required to pump it.
  • EXAMPLE 1 In a 3 liter cylindrical reaction vessel 200 grams of cupric benzoate and 175 grams of magnesium benzoate were dissolved in 2.5 kilograms of benzoic acid at a temperature of 230 C. Then 250 liters of air and 200 liters of steam (both calculated at C. and 1 atm;,STP) per hour were continuously introduced into the solution at atmospheric pressure while the temperature was main-- tained at 230 C. to 235 C. The gas-vapor mixture discharged from the reaction vessel was passed into a fractionating column from the top of which a mixture of phenol and water was discharged. The benzoic acid dis- 7 prevent accumulation of the tar, 60 grams of liquid reac-.
  • the oil phase having a viscosity of 107 centipoises was separated off continuously at 150 C.
  • EXAMPLE 3 2.7 kilograms ofthe tarmixture from the storage tank of Example 2 was mixed with 0.48 kilogram of aromatic hydrocarbon residue boiling above 200 C. and obtained in the refining of mineral oil. The resulting mixture was The procedure of Example 1 for preparing phenol was repeated except that 50 grams of anthracene oil per hour were charged into the reaction vessel and 110 grams of liquid reaction mixture per hour (rather than 60 grams per hour) were discharged .from the reaction vessel and introduced into the storage tank.
  • T0 recover non-converted benzoic acid 4.3 kilograms of the reaction mixture was taken from the storage tank and extracted with 12 kilograms of water at C. and a pressure of 6 atm. No creosote oil was used in this extraction since anthracene oil was already present.
  • the benzoic acid was recovered from the aqueous extract.
  • the oil phase separated off amounted to l kilogram and contained 0.7 kilogram of tarry by-product and had.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US214209A 1962-06-04 1962-08-02 Tar removal in phenol process Expired - Lifetime US3349134A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL279255 1962-06-04

Publications (1)

Publication Number Publication Date
US3349134A true US3349134A (en) 1967-10-24

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ID=19753874

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US214209A Expired - Lifetime US3349134A (en) 1962-06-04 1962-08-02 Tar removal in phenol process

Country Status (5)

Country Link
US (1) US3349134A (fr)
BE (1) BE633115A (fr)
CH (1) CH449047A (fr)
ES (1) ES288667A1 (fr)
GB (1) GB961287A (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929909A (en) * 1970-01-17 1975-12-30 Stamicarbon Process for the preparation of a phenol from a benzenemonocarboxylic acid
US3929911A (en) * 1970-01-17 1975-12-30 Stamicarbon Preparation of a phenol from a benzenemonocarboxylic acid
US4094909A (en) * 1976-02-28 1978-06-13 Stamicarbon, B.V. Process for the decarboxylation-oxidation of benzoic acid compounds
CN109355083A (zh) * 2018-11-26 2019-02-19 中冶焦耐(大连)工程技术有限公司 一种焦油减压蒸馏采三混馏分的工艺及系统

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL9201481A (nl) * 1992-08-20 1994-03-16 Dsm Nv Werkwijze voor de verwijdering van teer uit een fenolbereidingsproces.

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB108938A (en) * 1916-10-04 1917-08-30 Henri Terrisse Improvements in or relating to the Manufacture of Phenol.
US2727926A (en) * 1954-01-08 1955-12-20 Dow Chemical Co Catalytic oxidation of armoatic carboxylic acids to phenols
US2764587A (en) * 1954-01-08 1956-09-25 Dow Chemical Co Phenols from certain carboxylic acids
US2766294A (en) * 1952-05-19 1956-10-09 California Research Corp Process for preparing monohydroxy aromatic compounds from aromatic carboxylic acids
US2954407A (en) * 1957-10-21 1960-09-27 Dow Chemical Co Process for converting aryl carboxylic acids to phenols
US3130235A (en) * 1960-11-10 1964-04-21 Dow Chemical Co Method of removing tar from phenol reactor contents

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB108938A (en) * 1916-10-04 1917-08-30 Henri Terrisse Improvements in or relating to the Manufacture of Phenol.
US2766294A (en) * 1952-05-19 1956-10-09 California Research Corp Process for preparing monohydroxy aromatic compounds from aromatic carboxylic acids
US2727926A (en) * 1954-01-08 1955-12-20 Dow Chemical Co Catalytic oxidation of armoatic carboxylic acids to phenols
US2764587A (en) * 1954-01-08 1956-09-25 Dow Chemical Co Phenols from certain carboxylic acids
US2954407A (en) * 1957-10-21 1960-09-27 Dow Chemical Co Process for converting aryl carboxylic acids to phenols
US3130235A (en) * 1960-11-10 1964-04-21 Dow Chemical Co Method of removing tar from phenol reactor contents

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929909A (en) * 1970-01-17 1975-12-30 Stamicarbon Process for the preparation of a phenol from a benzenemonocarboxylic acid
US3929911A (en) * 1970-01-17 1975-12-30 Stamicarbon Preparation of a phenol from a benzenemonocarboxylic acid
US4094909A (en) * 1976-02-28 1978-06-13 Stamicarbon, B.V. Process for the decarboxylation-oxidation of benzoic acid compounds
CN109355083A (zh) * 2018-11-26 2019-02-19 中冶焦耐(大连)工程技术有限公司 一种焦油减压蒸馏采三混馏分的工艺及系统
CN109355083B (zh) * 2018-11-26 2024-05-14 中冶焦耐(大连)工程技术有限公司 一种焦油减压蒸馏采三混馏分的工艺及系统

Also Published As

Publication number Publication date
BE633115A (fr) 1963-12-02
CH449047A (de) 1967-12-31
ES288667A1 (es) 1963-08-01
GB961287A (en) 1964-06-17

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