US3335160A - Process for the continuous manufacture of substantially acetic acidcontaining mixtures of low molecular weight fatty acids by paraffin oxidation - Google Patents

Process for the continuous manufacture of substantially acetic acidcontaining mixtures of low molecular weight fatty acids by paraffin oxidation Download PDF

Info

Publication number
US3335160A
US3335160A US188220A US18822062A US3335160A US 3335160 A US3335160 A US 3335160A US 188220 A US188220 A US 188220A US 18822062 A US18822062 A US 18822062A US 3335160 A US3335160 A US 3335160A
Authority
US
United States
Prior art keywords
liquid
mixtures
reactor
fatty acids
flow reactor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US188220A
Other languages
English (en)
Inventor
Sennewald Kurt
Vogt Wilhelm
Erpenbach Heinz
Joest Herbert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Knapsack AG
Original Assignee
Knapsack AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Knapsack AG filed Critical Knapsack AG
Application granted granted Critical
Publication of US3335160A publication Critical patent/US3335160A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/243—Tubular reactors spirally, concentrically or zigzag wound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/2435—Loop-type reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00162—Controlling or regulating processes controlling the pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00164—Controlling or regulating processes controlling the flow
    • B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • the present invention relates to a process for the manufacture of substantially acetic acid-containing mixtures of saturated fatty acids of low molecular Weight by oxidation of paraflinic hydrocarbons having more than 2, preferably 4 to 8 carbon atoms, or mixtures thereof in the liquid phase at an elevated temperature and under pressure with oxygen or oxygen-containing gas mixtures.
  • the invention also provides an apparatus suitable for use in carrying out the process.
  • parafiinic hydrocarbons can be oxidized in the liquid phase with oxygen or an oxygen-containing gas, advantageously air, to fatty acids of low molecular Weight.
  • the starting materials used include, for example, mixtures of hydrocarbons having 4 to 8 carbon atoms which consist substantially of straight chained and branched paraflins, that may include a small proportion of cyclo-parafiins and aromatic hydrocarbons, and which can be obtained by distillation of petroleum.
  • the processes hitherto proposed and used industrially are carried out at an elevated temperature in the presence or absence of a catalyst in cylindrical high pressure reactors, the reaction mixture being sometimes moderately cycled by using some type of a thermo-siphon or a mammoth pump.
  • the yield of fatty acid calculated on the amount of carbon used, and more especially the space-time yield of fatty acid obtained, can be substantially improved in the manufacture of substantially acetic acid-containing mixtures of saturated fatty acids of low molecular weight by oxidation of parafiinic hydrocarbons having more than 2, preferably 4 to 8 carbon atoms, or mixtures thereof in the liquid phase at an elevated temperature and under pressure with oxygen or oxygen-containing gas mixtures.
  • the mixture of hydrocarbons, their oxidation products and oxygen-containing gas is circulated through a flow reactor with the aid of pumps at a velocity of flow of at least 50 cm./sec., the circulated reaction mixture is separated into liquid and off-gas and a portion of the liquid is continuously Withdrawn from the cycle in known manner and processed by distillation.
  • the first runnings and last runnings of the fatty acid fraction admixed with fresh hydrocarbon are introduced again into the cycle.
  • the apparatus used for carrying out the present process comprises a flow reactor which may be composed of a plurality of straight, series-connected pipe sections or have the form of a tubular coil.
  • the tubes may be provided in the interior with disturbing means, if desired, in order to still improve the intended intense turbulent mixing of gas with liquid.
  • no such States Patent auxiliary means are necessary to produce such intense and turbulent mixing.
  • the reaction tubes are jacketed; the jacket is charged with condensed steam maintained under pressure whereby the desired temperatures can be produced, i.e., by heating to initiate the reaction or by cooling to dissipate the reaction heat.
  • the steam generated may also be used in other zones of the apparatus.
  • the residence time of the reaction mixture consisting of the hydrocarbons, their oxidation prodnets and oxygen containing gas, in the flow reactor varies, per passage, between 10 and seconds, advantageously 20 and 50 seconds.
  • the mixture leaving the flow reactor is conveyed to a separator from which the off-gas is removed through a gas cooler.
  • the proportion of hydrocarbons included in the off-gas are recovered by washing with diesel oil.
  • the separator wherein the reaction liquid must rapidly be circulated in order to produce turbulent mixing, the mixture is not separated into two liquid phases. A portion of the reaction mixture in the separator is branched off for distillation. At the same time, a corresponding proportion of mixture to be oxidized is introduced into the reactor so that the level of liquid in the separator is kept constant.
  • the portion continuously branched off the cycled mixture for being worked up amounts to 1 to 15% by volume, preferably 4 to 10% by volume, of the total quantity of liquid circulated per hour by pumping.
  • the preferred oxygen-containing gas is air, which may be enriched with oxygen as desired. Mixtures of oxygen with inert gases may also be used.
  • the gas is used in a proportion such that the off-gas, after removal of all constituents condensable up to 20 C. and after the diesel oil wash, contains a maximum of 6%, advantageously 2 to 3%, oxygen.
  • the oxidation is carried out under a pressure of 40 to 60 atmospheres, preferably 45 to 50 atmospheres. Higher or lower pressures do not remarkably influence the course of the reaction.
  • the optimum temperature to be used for carrying out the oxidation varies between about and 200 C., advantageously and 180 C. Higher temperatures favor for the same residence time the formation of carbon dioxide, lower temperatures retard the velocity of oxidation.
  • the process of this invention yields more than 20% more fatty acid or more than 10% more fatty acid, calculated on the carbon used, and a 4 to 6 times greater space-time yield as compared with conventional processes and own tests carried out in a cylindrical reactor with and Without thermo-siphon circulation.
  • the process of this invention involves, inter alia, the advantage that no residues are obtained.
  • FIG. 1 represents the flow reactor and hence the oxidation Zone comprising several vertical tubes connected in series which are jacketed to receive the condensed steam which is used for heating or cooling.
  • the oxygen-containing gas is supplied through line 2 and the fresh hydrocarbon is supplied through line 3, the two components being introduced jointly through line 4 into flow reactor 1.
  • circulating pump 5 so great a proportion of reaction mixture is circulated through reactor 1 and separator 6 that the velocity of flow of the gas-liquid mixture is at least 50 cm./sec.; the difference in pressure between the inlet and outlet of the flow reactor is about 2 to 10 atmospheres absolute, preferably 4 to 6 atmospheres absolute.
  • the mixture circulated is also introduced into the reactor through line 4.
  • the residence time for one single passage through the fiow reactor amounts to 10 to 100 seconds, preferably 20 to 50 seconds.
  • the reaction mixture leaving flow reactor 1 travels into separator 6 from which the off-gas is removed through a gas cooler 7.
  • the off-gas freed from all products condensable up to 20 C. contains especially carbon monoxide, carbon dioxide and nitrogen when air was used as oxidizing agent.
  • the off-gas is then subjected still under pressure to the diesel oil wash at 8 where lowboiling oxidation products and hydrocarbons are absorbed.
  • the off-gas is then released at 13.
  • the diesel oil is freed in stripping column 9 from these low-boiling constituents which are returnedto the reactor through lines 10 and 3 into which a cooler is inserted.
  • a part of the reaction mixture obtained in separator 6 is removed through line 11 for distillation.
  • the same volume of mixture to be oxidized is introduced into the flow reactor through line 3 so that the liquid in separator 6 is maintained at a constant level.
  • the reaction product withdrawn is processed by distillation in a manner such that the constituents included in the reaction mixture which boil at a temperature lower than the C toC -acids and the higher boiling residue are returned into the reactor through lines 12 and 3.
  • the C to C -acids are the desired reaction product. Residual products are not obtained in the process.
  • test 4 a conventional process was used for comparison.
  • Example A mixture of 48% n-parafimic hydrocarbons and 48.4% isoparafiinic hydrocarbons was used as starting material.
  • the composition of the mixture in weight percent was as follows:
  • n-butane 1.0 n-pentane 17.3 i-pentane 10.9 n-hexane 29.0 2,2-dimethylbutane 0.5 2,3-dimethylbutane 15.9 B-methylpentane 13.0 n-heptane 0.7 2,4-dimethylpentane 0.5 2,2,3-trimethylbutane 5.9 2,3-dimethylpentane 0.8 B-methylhexane 0.9 Benzene 1.1 Other ingredients 2.3
  • the mixture had a mean carbon content of 84%, corresponding to a C-number of 7 per 100 g. hydrocarbon.-
  • the flow reactor 1 consisted of 10 stainless steel tubes having an internal diameter of 9 mm. and a length of 3.1 m., corresponding to a total capacity of 1.97 liter.
  • the air and liquid admission lines 4 were disposed at the foot of the first tube.
  • the reactor was continuously supplied with fresh hydrocarbon through line 3 and with air through line 2.
  • the oxidation was carried out at 170 C. under a pressure of 45 kg./cm. Both the gaseous and liquid products were conveyed from the oxidation zone into separator 6 in which the gas was separated from the liquid.
  • a process for the manufacture of mixtures of saturated C fatty acids, the main constituent of said mixtures being acetic acid which comprises passing in the liquid phase a mixture of parafiinic hydrocarbons having 4 to 8 carbon atoms, their oxidation products and oxygen-containing gas through a tubular flow reactor with a velocity of flow of at least 50 cm./sec., at a residence time of between 10 and 100 seconds per passage through said reactor, at a temperature between and 200 C; and under a pressure between about 30 and 80 atmospheres, continuously separating the crude reaction mixture leaving said tubular flow reactor into liquid gas, recycling a portion of said liquid to said flow reactor, distilling the remainder of said liquid to separate the C fatty acids therefrom and recycling the first and last runnings of the distillation to said flow reactor admixed with fresh parafiinic hydrocarbons having 4 to 8 carbon atoms.

Landscapes

  • 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)
US188220A 1961-04-19 1962-04-17 Process for the continuous manufacture of substantially acetic acidcontaining mixtures of low molecular weight fatty acids by paraffin oxidation Expired - Lifetime US3335160A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEK43506A DE1149708B (de) 1961-04-19 1961-04-19 Verfahren und Vorrichtung zur kontinuierlichen Herstellen von vorwiegend Essigsaeureenthaltenden Gemischen niedermolekularer Fettsaeuren durch Paraffinoxydation

Publications (1)

Publication Number Publication Date
US3335160A true US3335160A (en) 1967-08-08

Family

ID=7223139

Family Applications (1)

Application Number Title Priority Date Filing Date
US188220A Expired - Lifetime US3335160A (en) 1961-04-19 1962-04-17 Process for the continuous manufacture of substantially acetic acidcontaining mixtures of low molecular weight fatty acids by paraffin oxidation

Country Status (5)

Country Link
US (1) US3335160A (fr)
BE (1) BE616645A (fr)
DE (1) DE1149708B (fr)
GB (1) GB1007703A (fr)
NL (1) NL277161A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5385712A (en) * 1993-12-07 1995-01-31 Sprunk; Darren K. Modular chemical reactor
US5779994A (en) * 1995-10-16 1998-07-14 Bayer Aktiengesellschaft Tubular reactor
CN115106024A (zh) * 2022-07-04 2022-09-27 山东飞扬化工有限公司 一种混流反应器和混流反应设备及其用于生产碳酸酯的方法

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2734067A (en) * 1956-02-07 Hydrocarbon oxidation
GB757309A (en) * 1952-04-25 1956-09-19 Oxirane Ltd The manufacture of polyoxyalkylene glycols and their mono-ethers
US2770637A (en) * 1952-09-04 1956-11-13 Celanese Corp Production of oxygenated hydrocarbons
US2776309A (en) * 1954-02-16 1957-01-01 Sinclair Refining Co Foots oil oxidate composition
US2800504A (en) * 1952-10-15 1957-07-23 Distillers Co Yeast Ltd Production of lower aliphatic acids
US2800505A (en) * 1952-10-15 1957-07-23 Distillers Co Yeast Ltd Production of aliphatic acids
US2800506A (en) * 1953-04-25 1957-07-23 Distillers Co Yeast Ltd Production of aliphatic acids
US2825740A (en) * 1953-10-07 1958-03-04 Distillers Co Yeast Ltd Production of acetic acid
US2926191A (en) * 1956-05-22 1960-02-23 Distillers Co Yeast Ltd Chemical process
US2929690A (en) * 1956-04-27 1960-03-22 Whiting Corp Apparatus for removing impurities from vapors released in evaporation process
US3057699A (en) * 1958-03-24 1962-10-09 Boldon Continuous closed circuit apparatus for rendering animal matter

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2734067A (en) * 1956-02-07 Hydrocarbon oxidation
GB757309A (en) * 1952-04-25 1956-09-19 Oxirane Ltd The manufacture of polyoxyalkylene glycols and their mono-ethers
US2770637A (en) * 1952-09-04 1956-11-13 Celanese Corp Production of oxygenated hydrocarbons
US2800504A (en) * 1952-10-15 1957-07-23 Distillers Co Yeast Ltd Production of lower aliphatic acids
US2800505A (en) * 1952-10-15 1957-07-23 Distillers Co Yeast Ltd Production of aliphatic acids
US2800506A (en) * 1953-04-25 1957-07-23 Distillers Co Yeast Ltd Production of aliphatic acids
US2825740A (en) * 1953-10-07 1958-03-04 Distillers Co Yeast Ltd Production of acetic acid
US2776309A (en) * 1954-02-16 1957-01-01 Sinclair Refining Co Foots oil oxidate composition
US2929690A (en) * 1956-04-27 1960-03-22 Whiting Corp Apparatus for removing impurities from vapors released in evaporation process
US2926191A (en) * 1956-05-22 1960-02-23 Distillers Co Yeast Ltd Chemical process
US3057699A (en) * 1958-03-24 1962-10-09 Boldon Continuous closed circuit apparatus for rendering animal matter

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5385712A (en) * 1993-12-07 1995-01-31 Sprunk; Darren K. Modular chemical reactor
US5779994A (en) * 1995-10-16 1998-07-14 Bayer Aktiengesellschaft Tubular reactor
CN115106024A (zh) * 2022-07-04 2022-09-27 山东飞扬化工有限公司 一种混流反应器和混流反应设备及其用于生产碳酸酯的方法
CN115106024B (zh) * 2022-07-04 2024-04-16 山东飞扬化工有限公司 一种混流反应器和混流反应设备及其用于生产碳酸酯的方法

Also Published As

Publication number Publication date
BE616645A (fr) 1962-08-16
NL277161A (fr)
DE1149708B (de) 1963-06-06
GB1007703A (en) 1965-10-22

Similar Documents

Publication Publication Date Title
US2265948A (en) Catalytic oxidation of lower aliphatic hydrocarbons
US2565087A (en) Process for oxidation of cycloaliphatic compounds
US3071601A (en) Oxidation of propylene
US2766273A (en) Esterification of acids
US2514966A (en) Refining and concentrating crude unsaturated aldehydes by extractive distillation
US3293292A (en) Butane oxidation
US2557281A (en) Oxidation op petroleum cyclohexane
US4032563A (en) Process for the recovery of high purity diesters of terephthalic or isophthalic acids
US2514967A (en) Refining and concentrating crude unsaturated aldehydes
US2452741A (en) Production of dibasic acids
US3335160A (en) Process for the continuous manufacture of substantially acetic acidcontaining mixtures of low molecular weight fatty acids by paraffin oxidation
US4156632A (en) Process for the separation of water from gas mixtures formed in the manufacture of vinyl acetate
US2800506A (en) Production of aliphatic acids
US3472630A (en) Combination of apparatus elements for production and recovery of distillable aromatic acid
US2696499A (en) Preparation of toluic acids
US2926191A (en) Chemical process
US1877291A (en) Continuous method of producing esters from olefins
US2287125A (en) Oxidation of low molecular weight hydrocarbons in liquid phase and catalyst therefor
US2800504A (en) Production of lower aliphatic acids
US2527824A (en) Manufacture of xylene isomers
US3196182A (en) Oxidation of hydrocarbons
US2659746A (en) Oxidation process
US2800505A (en) Production of aliphatic acids
US2772305A (en) Oxidation of toluate esters and xylene mixtures
US2862854A (en) Purification of acetic acid employing hydroxylamine acetate as purifying agent