GB777038A - Improvements in or relating to method of carrying out homogeneous vapor phase reactions - Google Patents

Improvements in or relating to method of carrying out homogeneous vapor phase reactions

Info

Publication number
GB777038A
GB777038A GB20269/53A GB2026953A GB777038A GB 777038 A GB777038 A GB 777038A GB 20269/53 A GB20269/53 A GB 20269/53A GB 2026953 A GB2026953 A GB 2026953A GB 777038 A GB777038 A GB 777038A
Authority
GB
United Kingdom
Prior art keywords
reaction
solids
zones
fluidized
alcohols
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
Application number
GB20269/53A
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.)
ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
Esso Research and Engineering Co
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 Exxon Research and Engineering Co, Esso Research and Engineering Co filed Critical Exxon Research and Engineering Co
Publication of GB777038A publication Critical patent/GB777038A/en
Expired legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/26Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
    • B01J8/28Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations the one above the other
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1836Heating and cooling the reactor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/34Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with stationary packing material in the fluidised bed, e.g. bricks, wire rings, baffles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00115Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
    • B01J2208/00132Tubes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

<PICT:0777038/IV(b)/1> A non-catalytic homogeneous vapour-phase reaction, e.g. the partial oxidation of hydrocarbons, is carried out by passing the reactants alternately through reaction zones, which contain substantially no solid particles, and quenching zones which are contiguous with the reaction zones and which contain a dense fluidized mass of inert solid particles. The alternate reaction and quenching zones may be formed by producing slug flow in the reactor, i.e. by passing the reactants upwardly through the mass of finely divided inert solids at such a velocity with respect to the particle size and density of the solids and the diameter of the reaction vessel that the mass is continuously maintained in the form of a fluidized bed comprising bubbles of appreciable size bounded at their vertical extremities by a fluidized mass of the finely divided solids and surrounded at their horizontal extremities by a wall of the reaction vessel or by a substantially vertical baffle within the reaction vessel; the gases react within the bubbles and the reaction products are quenched by passing into the surrounding fluidized solids. Alternatively, the alternate reaction and quenching zones may be formed by separate dense fluidized beds and substantially solid-free spaces above the beds. In the apparatus shown, preheated and vaporized hydrocarbon is introduced at 20 and passes through grid 23; oxygen enters via pipes 21 and perforations 21a, 21b . . . The reactants and inert solids pass upward in slug flow through vertical tubes 27 provided in the reaction vessel. The fluidized solids descend through regions 28 without slug flow. Pipes 26 are provided for circulation of a cooling medium, e.g. water, steam, or oil. Reaction products are withdrawn at 22. In Fig. 2 (not shown), the reaction vessel contains a plurality of shallow dense fluidized beds on superimposed trays separated by gas-phase zones where reaction takes place; the fluidized beds do not form bubbles and are used for quenching the reaction products; the oxidizing gas may be introduced into the fluidized beds for preheating and distribution. Suitable contact times are 0.1-10 seconds, and the preferred oxygen to hydrocarbon mol. ratio is 0.3-1.5; reaction temperature may be 275-480 DEG C. and reaction pressure 0.15 p.s.i.g. or higher; steam or nitrogen may be present as a diluent. Suitable inert solids are sand, glass beads, clays, alumina, coke, carbon powder or granules, powdered copper, nickel or aluminium and steel or iron spheres; the diameter of the particles may be 40-1000 microns, and when bubbles are to be formed, preferably 40-220 microns. Specified hydrocarbon reactants are n-heptane, light and heavy naphthas, normal or monomethyl substituted paraffins of 5-16 carbon atoms, lower paraffins, olefins, octene-2, cyclohexane, methylcyclopentane and methylcyclohexane. The process results in the upgrading of the hydrocarbons for fuel purposes, or the formation of C1-C3 aldehydes, acrolein, ketones, alcohols, monocyclic ethers, and olefins. In the production of oxygenated compounds, the reaction product is cooled and forms a water layer and a hydrocarbon layer; gum-forming aldehydes in the hydrocarbon layer may be converted by light hydrogenation to alcohols or by dehydration to olefins; aldehydes and ketones in the water layer may be hydrogenated to alcohols. Examples and tables give details of the oxidation of n-heptane and solvent and heavy naphtha using sand and glass beads as the inert solids. The process may also be used for the selective oxidation of alcohols, ketones, aldehydes and aliphatic amines, ethers and esters, and for halogenations such as chlorinations, oxidations using nitrogen tetroxide as oxygen carrier, decomposition of peroxides and hydroperoxides, sulphurizations involving gaseous sulphur and hydrocarbons, and reactions involving acetylene. When using a plurality of shallow fluidized beds separated by reaction zones, different reactions may be carried out in sequence, e.g. oxidation in the lower stages and dehydrogenation or dehydration in the upper stages using an alumina or chromia catalyst.ALSO:<PICT:0777038/III/1> A non-catalytic homogenous vapour-phase reaction, e.g. the partial oxidation of hydrocarbons, is carried out by passing the reactants alternately through reaction zones, which contain substantially no solid particles, and quenching zones which are contiguous with the reaction zones and which contain a dense fluidized mass of inert solid particles. The alternate reaction and quenching zones may be formed by producing slug flow in the reactor, i.e. by passing the reactants upwardly through the mass of finely divided inert solids at such a velocity with respect to the particle size and density of the solids and the diameter of the reaction vessel that the mass is continuouly maintained in the form of a fluidized bed comprising bubbles of appreciable size bounded at their vertical extremities by a fluidized mass of the finely divided solids and surrounded at their horizontal extremities by a wall of the reaction vessel or by a substantially vertical baffle within the reaction vessel; the gases react within the bubbles and the reaction products are quenched by passing into the surrounding fluidized solids. Alternatively, the alternate reaction and quenching zones may be formed by separate dense fluidized beds and substantially solid-free spaces above the beds. In the apparatus shown, preheated and vaporized hydrocarbon is introduced at 20 and passes through grid 23; oxygen enters via pipes 21 and perforations 21a, 21b... The reactants and inert solids pass upward in slug flow through vertical tubes 27 provided in the reaction vessel. The fluidized solids descend through regions 28 without slug flow. Pipes 26 are provided for circulation of a cooling medium, e.g. water, steam, or oil. Reaction products are withdrawn at 22. In Fig. 2 (not shown), the reaction vessel contains a plurality of shallow dense fluidized beds on superimposed trays separated by gas phase zones where reaction takes place; the fluidized beds do not form bubbles and are used for quenching the reaction products; the oxidizing gas may be introduced into the fluidized beds for preheating and distribution. Suitable contact times are 0.1-10 seconds, and the preferred oxygen to hydrocarbon mol ratio is 0.3-1.5; reaction temperature may be 270-480 DEG C. and reaction pressure 0-15 p.s.i.g. or higher; steam or nitrogen may be present as a diluent. Suitable inert solids are sand, glass beads, clays, alumina, coke, carbon powder or granules, powdered copper, nickel, or aluminium, and steel or iron spheres; the diameter of the particles may be 40-1000 microns, and when bubbles are to be formed, preferably 40-220 microns. Specified hydrocarbon reactants are n-heptane, light and heavy naphthas, normal or mono-methyl substituted paraffins of 5-16 carbon atoms, lower paraffins. olefins, octene-2, cyclohexane, methylcyclopentane, and methylcyclohexane. The process results in the upgrading of the hydrocarbons for fuel purposes, or the formation of C1-C3 aldehydes, acrolein, ketones, alcohols, monocyclic ethers, and olefins. In the production of oxygenated compounds, the reaction product is cooled and forms a water layer and a hydrocarbon layer; gum-forming aldehydes in the hydrocarbon layer may be converted by light hydrogenation to alcohols or by dehydration to olefins; aldehydes and ketones in the water layer may be hydrogenated to alcohols. Examples and tables give details of the oxidation of n-heptane and solvent and heavy naphtha using sand and glass beads as the inert solids. The process may also be used for the selective oxidation of alcohols, ketones, aldehydes, and aliphatic amines, ethers, and esters, and for halogenations oxidations using nitrogen tetroxide as oxygen carrier, decomposition of peroxides and hydroperoxides, sulphurizations involving gaseous sulphur and hydrocarbons, and reactions involving acetylene. When using a plurality of shallow fluidized beds separated by reaction zones, different reactions may be carried out in sequence, e.g. oxidation in the lower stages and dehydrogenation or dehydration in the upper stages using an alumina or chromia catalyst.
GB20269/53A 1953-02-27 1953-07-21 Improvements in or relating to method of carrying out homogeneous vapor phase reactions Expired GB777038A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
BE526630X 1953-02-27

Publications (1)

Publication Number Publication Date
GB777038A true GB777038A (en) 1957-06-19

Family

ID=22139591

Family Applications (1)

Application Number Title Priority Date Filing Date
GB20269/53A Expired GB777038A (en) 1953-02-27 1953-07-21 Improvements in or relating to method of carrying out homogeneous vapor phase reactions

Country Status (2)

Country Link
BE (1) BE526630A (en)
GB (1) GB777038A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116408128A (en) * 2023-06-09 2023-07-11 西南林业大学 Method for preparing Cu-N doped gum carbon catalyst by adopting bitter cherry gum and application

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1220419B (en) * 1959-02-07 1966-07-07 Exxon Research Engineering Co Process for carrying out the partial oxidation of organic compounds in the vapor state in the presence of heat-absorbing solids

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116408128A (en) * 2023-06-09 2023-07-11 西南林业大学 Method for preparing Cu-N doped gum carbon catalyst by adopting bitter cherry gum and application
CN116408128B (en) * 2023-06-09 2023-08-04 西南林业大学 Method for preparing Cu-N doped gum carbon catalyst by adopting bitter cherry gum and application

Also Published As

Publication number Publication date
BE526630A (en) 1956-08-17

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