Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
  • B01F23/20—Mixing gases with liquids
  • B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
  • B01F23/232—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using flow-mixing means for introducing the gases, e.g. baffles
  • B01F23/2323—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using flow-mixing means for introducing the gases, e.g. baffles by circulating the flow in guiding constructions or conduits
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
  • B01F25/40—Static mixers
  • B01F25/42—Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
  • B01F25/43—Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction
  • B01F25/433—Mixing tubes wherein the shape of the tube influences the mixing, e.g. mixing tubes with varying cross-section or provided with inwardly extending profiles
  • B01F25/4331—Mixers with bended, curved, coiled, wounded mixing tubes or comprising elements for bending the flow
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F2215/00—Auxiliary or complementary information in relation with mixing
  • B01F2215/04—Technical information in relation with mixing
  • B01F2215/0413—Numerical information
  • B01F2215/0418—Geometrical information
  • B01F2215/0431—Numerical size values, e.g. diameter of a hole or conduit, area, volume, length, width, or ratios thereof

Definitions

• the invention relates to method for dry hydrochlorination of mass from glycerol hydrochlorination with hydrochloric acid and device for dry hydrochlorination of mass from glycerol hydrochlorination with hydrochloric acid.
• Hydrochlorination of glycerol at 105 ⁇ 120°C in the presence of concentrated acetic acid as a catalyst is a commonly known method for synthesis of dichloropropanol isomers mixture of high concentration.
• the technological process includes the following stages: preparation of glycerol-acetic acid mixture, synthesis of dichloropropanols, neutralization of the post-reaction mass, and separation of pure dichloropropanols by rectification.
• composition of the post-reaction mass of glycerol hydrochlo- rination, in which contents of sum of dichloropropanol isomers is higher than 10% molar and lower than 98% molar, is claimed.
• a novelty in hydrochlorination method of glycerol consists in carrying out the reaction under pressure from 2.5 to 44 bar at 50 ⁇ 140°C.
• catalysts of carboxylic acids, carboxylic acid anhydrides, acid chlorides, esters, lactones, lactans groups are used.
• carboxylic acids acids containing from 1 to 60 carbon atoms in the molecule are claimed.
• carboxylic acid anhydrides acetic acid anhydride, propionic acid anhydride, butyric acid anhydride etc. are claimed.
• From among of acid chlorides 6-chlorohexanoic acid, 5- chloropentanoic acid, 4-chlorobutyric acid etc.
• esters of glycerol esters of ethylene glycol and esters of poly(propylene glycol) with carboxylic acids are claimed.
• lactones and lactans ⁇ -caprolactone, ⁇ -butyllactone, ⁇ - valerolactone are claimed. While the reaction is being carried out, water forming as a result of it is not carried off, and the post-reaction mixture is subjected to distillations in order to separate the unreacted hydrogen chloride dissolved in water (hydrochloric acid), the concentrated reaction product being a mixture of 1,3- and 2,3 -dichloropropanol isomers, and a residue consisting mostly of polyglycerols and their esters.
• Patent application No. WO 2006/100317 claims utilization of metallic and non-metallic materials resistant to hydrochlorinating agents for production of equipment and piping for hydrochlorination reaction of polyols.
• metallic materials tantalum, zirconium, titanium, platinum and their alloys, alloys of molybdenum, nickel and copper, and also alloys of gold and silver are claimed; and among non-metallic materials, elastomers, thermoplastics, glass, ceramic, metalloceramic laminates, fireproof materials, self-curing agents, impregnated graphite, carbon, glass, enamel, porcelain and stoneware are claimed. These materials are resistant in the temperature range from 0 to 200°C.
• the invention according to Polish patent application No. P-383486 pertains to method of generation of a mixture of 1,3- and 2,3-dichloropropanols forming as a result of reaction of glycerol hydrochlorination with gaseous hydrogen chloride.
• the process is carried out in a cascade of four tank reactors with intersecting feeding of each reactor with gaseous hydro- gen chloride and serial flow of the liquid reacting mass through the reactors, in the presence of adipic acid as a catalyst.
• Time spent by the mixture in the reactors is selected in a way ensuring the assumed conversion level of glycerol after the reactor, and the assumed total contents of 1,2- and 1,3-dichlopropanols after the reactor; water from the reaction is collected together with a section of the formed mixture of 1,3- and 2,3-dichloropropanols in vapour phase from each of the cascade reactors, and separation of the concentrated product from the cascade reactor's decoction is carried out in a rectifying column with at least 28 theoretical plates, while the decoction is introduced on the plate between 10 and 18 theoretical plates from the bottom, and unreacted alpha- and beta-monochlorohydrins are returned to the reactor.
• the invention according to Polish patent application No. P-383486 presents a method of generation of a mixture of 1,3- and 2,3-dichloropropanols, a raw material for epichloro- hydrin production, of glycerol.
• Glycerol containing dissolved catalyst is introduced to an absorption column, and non-reacted gaseous hydrogen chloride from a flow reactor mixed with hydrogen chloride from condenser of a dehydration column is introduced in a coun- tercurrent.
• the flow of partially reacted glycerol from the absorption column is directed to a flow reactor, fresh gaseous hydrogen chloride is introduced in a countercurrent.
• Aim of the invention is to develop a more effective and more economic method and device for dry hydrochlorination of mass from glycerol hydrochlorination with hydrochloric acid.
• the method of dry hydrochlorination of mass from glycerol hydrochlorination with hydrochloric acid consists in the following:
• the mass from glycerol hydrochlorination with hydrochloric acid is introduced into the dispersion zone of a device for dry hydrochlorination, and the reaction is initiated by introduction of gaseous hydrogen chloride;
• a forced turbulent flow of the liquid mass with gaseous hydrogen chloride in the dispersion zone is formed until a diphase mixture is formed;
• the diphase mixture is introduced into the bubbling zone consisting of a column reactor of the device, tangentially in relation to its internal circumference;
• gaseous hydrogen chloride is introduced to the liquid mass in the dispersion zone in one, two or more points along its length, located between the point of the liquid mass introduction and the end of the dispersion zone, while introduction of gaseous hydrogen chloride to the liquid mass is realized by direct contact of connections of conduits with the mass and with hydrogen chloride.
• gaseous hydrogen chloride is introduced to the liquid mass in the dispersion zone in one, two or more points along its length, located between the point of the liquid mass introduction and the end of the dispersion zone, while introduction of gase- ous hydrogen chloride to the liquid mass is realized by use of static mixers.
• gaseous hydrogen chloride is introduced to the liquid mass in the dispersion zone in one, two or more points along its length, located between the point of the liquid mass introduction and the end of the dispersion zone, while introduction of gaseous hydrogen chloride to the liquid mass is realized by use of nozzles.
• the device for dry hydrochlorination of mass from glycerol hydrochlorination with hydrochloric acid is characterized in that the device includes a dispersion zone and a bubbling zone connected with it, while the bubbling zone consists of a column reactor.
• dispersion zone consists of an external pipe coil, with outlet connector pipe is connected with inlet connector pipe of the column reactor.
• the dispersion zone consists of an integrated pipe coil with inlet connector pipe, coiled on the external side of the column reactor, while the lower section of the integrated pipe coil is located inside the column reactor.
• cross-section area of the dispersion zone is of any shape.
• Another preferred feature of the invention consists in that the ratio of length of the dispersion zone formed of the external pipe coil or of the integrated pipe coil to the height of the column reactor is in the range from 15:1 to 25 : 1.
• the dispersion zone consists of an external casing enclosing the col- umn reactor, while the lower section of the external casing is connected with the interior of the column reactor, and the upper section has an inlet connection pipe preferably located tangentially to the surface of the column reactor.
• the dispersion zone is equipped along its length with one or more connector pipes supplying gaseous hydrogen chloride.
• dispersion zone is equipped with a static mixer or nozzles.
• Fig.1 shows the device for dry hydrochlorination of mass from glycerol hydrochlorination with hydrochloric acid with an external pipe coil
• Fig. 2 shows the device for dry hydrochlorination of mass from glycerol hydrochlorination with hydrochloric acid with an integrated pipe coil
• Fig. 3 shows the device for dry hydrochlorination of mass from glycerol hydrochlorination with hydrochloric acid with an external casing.
• the device (1) for dry hydrochlorination of mass from glycerol hydrochlorination with hydrochloric acid includes an external pipe coil (2) constituting dispersion zone, and a column reactor (3) constituting bubbling zone.
• the external pipe coil (2) consists of coils of the external pipe coil (4) with internal diameter D 2 and it is equipped with inlet connector pipe (II), via which mass from glycerol hydrochlorination with hydrochloric acid flows into the external pipe coil (2).
• the external pipe coil (2) is connected with the column reactor (3) via an outlet connector pipe (01).
• the external pipe coil (2) it is equipped with connector pipes (12, 13, 14), via which gaseous hydrogen chloride for hydrochlorination is supplied appropriately to the external pipe coil (2).
• gaseous-liquid mixture flows out of the external pipe coil (2) to the column reactor (3), where hydrochlorination of the mass from glycerol hydrochlorination with hydrochloric acid is being concluded.
• the post-reaction mass is carried off from the device (1) for dry hydrochlorination of mass from glycerol hydrochlorination with hydrochloric acid via lateral connector pipe (02), and non-reacted hydrogen chloride is carried off via connector pipe (03).
• the device (1) for dry hydrochlorination of mass from glycerol hy- drochlorination with hydrochloric acid includes integrated pipe coil (5) constituting dispersion zone, and column reactor (3) constituting bubbling zone.
• the integrated pipe coil (5) consists of coils winding round the external casing of the column reactor (3) and it is equipped with inlet connector pipe (112), via which mass from glycerol hydrochlorination with hydrochloric acid flows into the integrated pipe coil (5).
• the integrated pipe coil (5) it is equipped with connector pipes (121, 131, 141), via which gaseous hydrogen chloride for hydrochlorination is supplied appropriately to the integrated pipe coil (5).
• gaseous-liquid mixture flows to the column reactor (3), where hydrochlorination of the mass from glycerol hydrochlorination with hydrochloric acid is being concluded.
• the post-reaction mass is carried off from the device (1) for dry hydrochlorination of mass from glycerol hydrochlorination with hydrochloric acid via lateral connector pipe (Oi l), and non-reacted hydrogen chloride is carried off via connector pipe (021).
• the device (1) for dry hydrochlorination of mass from glycerol hy- drochlorination with hydrochloric acid includes an external casing (6), constituting the dispersion zone, coiled around the tank reactor (3).
• the lower section of the external casing (6) is connected with the interior of the tank reactor (3), and the upper section is equipped with inlet connector pipe (112).
• the inlet connector pipe (112) in the upper section of the external casing (6) is located tan- gentially in relation to wall surface of the column reactor (3) and mass from glycerol hydrochlorination with hydrochloric acid flows via connector pipe to the interior of the external casing (6).
• the external casing (6) constituting the dispersion zone, coiled around the tank reactor (3), it is equipped with connector pipes (122, 132, 142), via which gaseous hydrogen chloride for hydrochlorination is supplied appropriately to the interior of the external casing (6). From the lower section of the external casing (6), gaseous-liquid mixture flows to the column reactor (3), where hydrochlorination of the mass from glycerol hydrochlorination with hydrochloric acid is being concluded.
• the post-reaction mass is carried off from the device (1) for dry hydrochlorination of mass from glycerol hydrochlorination with hydrochloric acid via lateral connector pipe (012), and non-reacted hydrogen chloride is carried off via connector pipe (022).
• the dispersion zone of gaseous hydrogen chloride and initiation of reaction in it is formed by forced turbulent flow of the liquid mass with gaseous hydrogen chloride in a cross- section of any shape, while the route of the turbulent flow of the liquid mass with gaseous hydrogen chloride may range from top to bottom at the external section of the column re- actor casing or be located outside the column reactor. Then, the diphase mixture flows from the bottom of the column reactor, tangentially in relation to its circumference, into the bubbling zone with free flow of gaseous bubbles upwards in a liquid column of defined height.
• Any shape of the cross-section area of turbulent flow of the liquid mass with gaseous hy- drogen chloride is circular cross-section, square cross-section, rectangular cross-section, triangular cross-section, trapezoidal cross-section, annular cross-section, or semicircular cross-section.
• the ratio of the dispersion zone length to the bubbling zone height is in the range from 20 to 1.
• the liquid mixture of non-reacted glycerol and monochlorohydrin isomers mixture in supplied in the topmost point of the dispersion zone of gaseous hydrogen chloride.
• Gaseous hydrogen chloride is introduced to the liquid mass in the dispersion zone in one, two or more points along its length, located between the point of the liquid mass introduction and the end of the dispersion zone, while introduction of gaseous hydrogen chloride to the liquid mass is realized by direct contact of connections of conduits with the mass and with hydrogen chloride, or by use of static mixers or nozzles.
• a device for dry hydrochlorination of mass from glycerol hydrochlorination with hydrochloric acid is shown for production scale of mixture of sum of dichloropropanol isomers 16000 t/year.
• the dispersion zone of gaseous hydrogen chloride and initiation of hydrochlorination in it consists of 24 coils of pipe coil with coil di- ameter of 900 mm.
• Mass from glycerol hydrochlorination with hydrochloric acid flows into pipe coil with internal diameter of 50 mm via connector pipe (II), and gaseous hydrogen chloride via connector pipes (12, 13 and 14) appropriately.
• Gas-liquid mixture flows out via connector pipe (01) to the column reactor, in which completion of hydrochlorination occurs.
• the connector pipes (13, 14 and 01) are positioned in relation to the connector pipe (12) in a way ensuring that the flow routes of the diphase mixture between the connector pipes (12 and 13, 13 and 14), and (14 and 01) were approximate.
• the connector pipe (15) in the column reactor is positioned tangentially in relation to its circumference. Diameter of the column reactor D is 800 mm, and height of the liquid column is 5200 mm.
• a device for dry hydrochlorination of mass from glycerol hydrochlorination with hydrochloric acid is shown for production scale of mixture of sum of dichloropropanol isomers 16000 t/year.
• Mass from glycerol hydrochlorination with hydrochloric acid flows into pipe coil with internal diameter of 50 mm via connector pipe (II), and gaseous hydrogen chloride - with mass divided into three flows independent - via connector pipes (12, 13 and 14).
• the liquid post-reaction mass flows out via connector pipe (011), and non-reacted hydrogen chloride - via connector pipe (021).
• a device for dry hydrochlorination of mass from glycerol hydrochlorination with hydrochloric acid is shown for production scale of mixture of sum of dichloropropanol isomers 16000 t/year, in which the dispersion zone of gaseous hydrogen chloride in the liquid mass, and the bubbling zone through the defined height of the liquid column are located in one device.
• the liquid mass is supplied via connector pipe (112), and gaseous hydrogen chloride - via connector pipes (122, 132 and 142). Dispersion of gaseous hydrogen chloride and initiation of reaction occurs in annular space with diameter ratio D z /D amounting to 1.125.
• the connector pipes (122, 132 and 142) are positioned relation to height of the dispersion zone of gaseous hydrogen chloride in the liquid mass in a way ensuring the heights between the connector pipes (122) and (132), (132) and (142), and (142) and the end of the dispersion zone are approximate.
• the ratio of height of the dispersion zone 3 ⁇ 4 to the bubbling zone height amounts to 0.50.
• the liquid post-reaction mass flows out via connector pipe (012), and non-reacted hydrogen chloride - via connector pipe (022).

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Dispersion Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Publications (1)

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Citations (7)

• 2011
  • 2011-04-11 PL PL394515A patent/PL218074B1/pl unknown
• 2012
  • 2012-03-18 WO PCT/PL2012/000013 patent/WO2012141602A1/en not_active Ceased

Patent Citations (9)

Non-Patent Citations (1)

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