PCT WORLD INTELLECTUAL, PROPERTY ORGANIZATION Tnemationa Butea 6 INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (61) International Patent Classification 6 CLIC 04 AL (11) International Publication Number: (43) International Publication Date: WO 97407187 27 February 1997 (27.02.97) (21) International Application Number: PCT/DK96100353 (22) International Filing Date: 21 August 1996 (21.08.96) (G0) Priority Data: ‘0928/95 21 August 1995 (21.08.95) DK (71) Applicant (for all designated States except US POUL "MOLLER LEDELSES- OG INGENIGRRADGIVNING APS (DK/DK]; Manelis Boulevard 38, 14, DK-8000 ‘Aathus C (DK). (72) Inventor; and (15) Inventor/Applicant (for US only): MOLLER, Poul {DK/DK}; Marselis Boulevard 38, 14, DK-8000 Aathus C (DK). (74) Agent: HOFMAN-BANG & BOUTARD, LEHMANN & REE. ‘AIS; Adelgade 15, DK-1304 Copenhagen K (DK). (Gt) Designated States: AL, AM, AT, AU, AZ, BB, BG, BR, BY, ‘CA, CH, CN, CU, CZ, DE, Di TL,1S, IP, KE, KG, KP, ‘With international search report In English translation (led in Danish). (G4) Title;A METHOD FOR SPLITTING OF FATS AND OTHER. hot 02 (7) Abstract [ESTERS BY HYDROLYSIS elycerine water ‘The present invention concems a method forthe sping of fats and other esters by hydrolysis at nearcrtcal temperatures and superritcal pressures, Under these temperature and pressure condi tions, the reaction will proceed in a homogeneous phase, and this ensures that the reaction proceeds considerably more rapidly than with the existing methods, and that it can be carried out in a reactor whichis considerably smaller than the previously used reactors, which reduces the process equipment cot.FOR THE PURPOSES OF INFORMATION ONLY ‘Codes used to identify States party tothe PCT on the front pages of pamphlets publishing intemationsl applications under the PCT. AM Arwen 6B nied Kingdon MW Mali AT Aaa CE Grogia MX Mero AU Aare ON Gunes NE Nee BS ator CR Gree NL Needs BE Belgian HU finery NO Rorway BF Butins Fo kind NZ New Zaed BG Bulgin 7 hy PL Pama BI besin Pes PP Perea BR Baal Ke Keys RO Roman BY elie KG Kyrpeun RU Rain dein cA Coat KP Democratic Pop's Repub. SD Sdn (CF Ceara Afican Rope sf Kors fede CG Gongs KR Reb of Kora SC Siemere CH Seamed KZ Kanth St Sbveus Gee ehie Heke 5k Slokin cH Cameco tk Silat SN Sere Ginn TR Lie 52 Smulins 3 Cassone UP Lithia ™ Cat Coch Repti EU Comamboas TG Top DE Gemny Wo Lee 1 Tyke DK Deana MC Moexo TT Td a Totes EE aoa MD Repub of Moons UA Unie Spin MG Maapucer UG Uns Pilg ML Mal US Uae Stes of Ames oko MN Monga U2 Usteiae GA Gabon MR Montais WN Vet Nemwo 97/07187 PCT/DK96/00383 10 15 20 25 30 35 A_method for splitting of fats and other esters by hy- drolysis The present invention concerns a method for the splitting of fats and other esters by hydrolysis at nearcritical temperatures and supercritical pressures. Fat splitting is the process wherein fats, which are fatty acid esters of glycerol, are split into their re- spective components fatty acid and glycerol. Thus, fat splitting makes it possible to recover and use fatty acid and glycerol e.g. for the synthesis of new compounds. Fatty acid may thus be used for the production of soap and candles. Today, various methods useful for the splitting of fats are known; one of these is hydrolysis. Fats or oils may be hydrolyzed or split into their fatty acid components and glycerol. The reaction proceeds in steps via diglycerides and monoglycerides. The complete reaction is illustrated by the following equation of re- action: RCOOCH: RCOOH CH:OH | | R'COOCH + 3H.0 © R'COOH + CHOH | | R'"COCCH: R' "COOH CH.OH wherein R, R' and R'' represent fatty acid chains of varying length and unsaturation degree. It has been found that only a minor part of the fat splitting takes place in the interface between water and fat, and that the fat splitting is essentially a ho-‘wo 9707187 PCT/DK96/00353 10 15 20 25 30 35 mogeneous reaction which takes place by the dissolution of water in the fat phase. The reaction proceeds slowly in the first step because of the low solubility of water in the fat phase. The reac- tion proceeds more rapidly in the following steps until equilibrium is attained. To complete the reaction, i.e. to shift the equilibrium to the right, it is necessary either to add water to the reaction mixture or to remove one of the reaction products glycerol and fatty acid or both reaction products. The rate of the reaction may be increased by increasing the temperature and the pressure, since this improves the solubility of water in the oil phase. Thus, an increase in the temperature from 150 °C to 220 °C increases the water solubility two to three times. To obtain a high re- action degree, the content of water and triglyceride (the reactants) in the fat-containing phase should be as high as possible and the content of fatty acids and glycerol (the reaction products) as low as possible. The mass transport between the two phases is thus of great importance to the reaction, as water is to be car- ried into the fat-containing phase and the reaction prod- ucts are to be carried into the water-containing phase. The presence of small amounts of mineral acids, such as sulphuric acid, or metal oxides, such as zinc or magne- sium oxide, accelerates the splitting reaction. The use of mineral acids, however, causes corrosion. This is not the case with the metal oxides. Various methods for the splitting of fats by hydrolysis are known. The oldest ones of these methods are charac- terized i.a, by their high consumption of energy, longwos707187 PCT(DK96/00353 10 15 20 25 30 35 reaction time (12 to 24 hours), poor quality of the reac- tion products and poor yields (80 to 85%). Further, reac- tion vessels of a diameter of up to 1.8 m and a height of up to 12 m, made of a corrosion-resistant material, are used for these methods. It is moreover necessary to use a form of mechanical stirring in the vessels to increase the mass transport between the phases and to add cata- lysts. It is moreover known to use enzymatic splitting of fats, where e.g. the enzyme lipase acts as a catalyst in the hydrolysis of the ester. This process has an optimum ef- fect at about 35 "C. However, the process has no commer- cial interest because of high costs and long reaction times. But it is the only process which can be used in connection with very temperature-sensitive fats and oils because of the low reaction temperature. The most commonly used and most effective method for fat splitting by hydrolysis is "the continuous process". The method uses high temperatures and pressures, which re- duces the reaction time. The reaction’ can be performed without the use of a catalyst in a counterflow reactor, but the reaction time may be reduced additionally by the use of a catalyst. The reactor used has a diameter from about 0.5 to 1.2 m and a height from 18 to 25 m and is made of a corrosion-resistant material. The reaction ves- sel can work at a pressure of up to about 5000 kPa (50 bars). The ratio of fat to water is 2-2.5:1 at a tempera- ture of 250 °C to 260 “C. In spite of these high parame ters, the reaction time is still considerable, 2 to 3 hours, and splitting degrees of up 99% can be achieved. However, the process requires huge process equipment costs, because the large reactors must be capable of withstanding the high pressures and corrosion (A.E. Bai- ley, Industrial Oil and Fat Products, 2nd edition 1951,‘wo 97/07187 PCT/DK96/00353, 10 15 20 25 30 35 P. 795-806; Bailey's Industrial Oil & Fat Products, 4th edition 1982, Ed. D. Swern, vol. 2, p. 97-113, ibid. 5th edition 1996, Ed. T.H. Hui, vol. 5, p. 40-43). As stated above, the reaction rate depends i.a. on the temperature and the pressure. Increasing temperature and Pressure increase the mutual solubility of the two Phases, and a homogeneous phase is formed. For coconut oil, this takes place at 293 °C and 8 MPa (80 bars) and for tallow at 321 "C and 12 MPa (120 bars). The use of SCF (supercritical fluid) in chemical proc- esses has been known for several years. At the critical point of water (T., Pz), T:= 374 °C and P. = 22.1 MPa (221 bars), the properties of the two phases water and water vapour are identical. Thus, the density about the critical point may be varied to be gas-like or water-like by changing the pressure. Also other properties, such as diffusivity, viscosity, dielectric constant and solubil- ity parameters may be varied. Viscosity, dielectric con- stant and solubility will thus be increased with increas- ing density. The diffusivity, however, decreases with in- creasing density. At the critical point, water has a den- sity of about 0.3 g/cm’ compared with 1 g/cm’ at normal temperatures and pressures. At the critical point, the dielectric constant of water is about 6 as compared with about 80 at normal temperatures and pressures. At this low dielectricity constant, water turns into a non-polar solvent and is capable of dissolving organic compounds. A pressure increase up to 34.0 MPa (340 bars) will in- crease the density from the critical value of 0.3 g/cm to 0.9 g/cm’, the dielectricity constant from about 6 to about 12 and the ion product from 10°'* to about 107". The concentrations of the hydrolysis-catalyzing H and OH ions will be increased by about 2.5 powers of ten. This makeswos07187 PCT/DK96/00353, 10 15 20 25 30 35 water autocatalytic (E.U. Franck, J. Chem. Thermo- dynamics, 1987, 19, p. 225-242; L.T. Boock et al., En~ deavour New Series, 1993, 17/4, p. 180-185). One object of the present invention is to provide a method for the splitting of fats and other esters by hy- drolysis, which method is faster than the existing methods. Another object of the invention is to provide a method for the splitting of fats and other esters, which method may be carried out in a reactor which is consid- erably smaller than the reactors previously used, thereby reducing the process equipment costs. This is achieved by the method of the invention which is characterized in that the hydrolysis is carried out at nearcritical temperatures and supercritical pressures. Nearcritical temperatures mean temperatures about the critical temperature of water. Supercritical pressures mean pressures above the critical pressure of water. Performance of the splitting at nearcritical temperatures and supercritical pressures ensures mutual miscibility of the fats and water in one phase, so that the interface between the phases, which is one of the most important obstacles to the reaction rate, disappears, thereby eliminating the transport resistances to the chemical re~ action. The reaction temperature and the high concentration of H and OH ions likewise contribute to increasing the reac- tion rate. In an embodiment of the method of the invention, the hy- drolysis is performed at a temperature in the range 300 to 500 “Cc and a pressure in the range 30 to 40 MPa (300wo9707187 PCT/DK96/00353 10 15 20 25 30 35 to 400 bars). When this temperature and pressure range is selected, the reaction time may be reduced to between 0.01 second and 10 minutes. In a further embodiment of the invention, the hydrolysis is performed at a temperature in the range 350 to 370 ‘C and a pressure in the range 32 to 40 MPa (320 to 400 bars). When this preferred temperature and pressure range is selected, the reaction time is between 0.02 second and 2 minutes. Thus, when the reaction time is reduced from the known 2 to 3 hours to about 2 minutes or less, the volume of the reactor may be reduced to 1/75 or less. This involves a considerable reduction in the costs of materials. Where the necessary reactor volume may be reduced to a few litres, the reactor can be omitted completely and be replaced by one of the heat exchangers which are used for the heating of the reaction mixture. To achieve splitting degrees of 99% or more, it is neces- sary that the reaction takes place in a number of steps with intermediate cooling to e.g. 250 °C and separation of the lipophilic and hydrophilic phases in a known manner. Preferably, the reaction takes place in three steps, with addition of water in each step, and the three aqueous glycerol solutions are joined in a liquid flow which is adiabitically brought back to atmospheric pressure. Because of the great pressure drop from e.g. 36 MPa (360 bars) to 0.1 MPa (1 bar), this must be done stepwise e.g. by flashing the total amount of glycerol water through 2 or 3 devices connected in series. The pressures in the various steps may e.g. be 5 MPa (50 bars) in the first step, 0.7 MPa (7 bars) in the second step, and 0.1 MPa (1 bar) in the third and last step. Thewo 9707187 PCT/DK96/00353, 10 15 20 25 30 35 formed liquid and vapour phases are concomitant and are passed to the main flow for common separation. Reaction times similar to those mentioned above may be obtained at lower temperatures and pressures by using a suitably selected catalyst. Preferred catalysts may be selected from the group consisting of salts of boric acid, silicic acid and phosphoric acid as well as silica or mixtures thereof. Particularly preferred salts of the above-mentioned acids are selected from the metals of the first and second main groups, in particular sodium, mag- nesium and calcium. A particularly preferred catalyst is sodium tetraborate. In the embodiment of the invention in which a catalyst is added, the method may be performed at a temperature in the range 250 to 370 °C and a pressure in the range 22.1 to 40 MPa (221 to 400 bars) with a concentration of the salts of about 0.1 M or less, preferably 300 to 320 “C, 22.1 to 40 MPa (221 to 400 bars) with a concentration of the salts in the range from about 0.001 M to about 0.005 M. In addition to being used for the splitting of fats, the method of the invention may also be used for the split~ ting of other types of esters. Thus, e.g. sterols may be released from their esters with essentially fatty acids in tall oil and concentrates thereof, such as the residue from the distillation of tall oil, called tall oil pitch. Sterols may hereby be recovered from a residue and may be used e.g. in the pharmaceutical industry. The invention will now be described more fully with ref- erence to the accompanying drawing, in which figure 1 shows a flow diagram of an embodiment according to thewo 9707187 PCT/DK96/00353 10 15 20 25 30 35 invention, and figure 2 shows a special embodiment of the heat exchanger 2b in figure 1. The splitting of the fat may take place in a continuous i-step system whose flow diagram is shown in figure 1. Via the pumps la and lb, fat and water, respectively, are conveyed continuously in the desired ratio to a mixer M, in which fat and water are mixed. From there, the mixture is passed through the heat exchangers 2a and 2b to the reactor 4. The heat exchangers may be constructed as double pipe heat exchangers with the mixture of fat and water innermost, optionally provided with static mixers en route (not shown). The mixture is heated in the first heat exchanger 2a by re-using heat in the product flow from the reactor 4. The mixture is heated to the reaction temperature concerned, e.g. with hot oil, in the second heat exchanger. The reaction temperature is kept constant in that a thermometer just after the heating zone con- trols the access of hot oil via the regulation valve 3. The reactor 4 is a long pipe having a volume which is adapted to the desired capacity and reaction time. Having given off its heat in the heat exchanger 2a, the product flow is conveyed through a stepwise pressure reduction from about 36 MPa to 0.1 MPa. This may take place via the Pressure reduction valves 5a, 5b and 5c, which ensure that the pressure is maintained at about 5 MPa in the flash container 6a, 0.7 MPa in the flash container 6b, and 0.1 MPa in the separating flask 7. The heavy glycerol water is separated from the lighter fat phase in the usual manner in the separating flask, and gases, if any, may leave the separating flask at the top. The heat ex- changer 8 cools the product flow to about 70 to 80 °C. The two liquid phases are processed in a traditional man- ner.wo 9707187 PCT/DK96/00353 10 15 20 25 30 35 In figure 2, the heat exchanger 2b, which heats the reac- tion mixture to the desired temperature, is shown as a double pipe heat exchanger with the reaction mixture in the inner pipe and the heating medium, e.g. hot oil, in the jacket. At the outlet of the heat exchanger zone, a thermometer or the like ensures that the temperature of the mixture is kept constant by controlling the access of the heating medium to the jacket via the valve 3. This embodiment is particularly suitable in the situation where the reactor, owing to the very rapid reaction, is so small that it may suitably be built together with the nearest heat exchanger 2b. The pipe with the reaction mixture may be extended to the desired volume, which cor- responds to the desired capacity and residence time. The extension, e.g. in the form of a holding cell, may thus replace the reactor 4 of figure 1. The following non-limiting examples illustrate the method of the invention in greater detail. Example 1 100 parts by weight of lard having a free fatty acid con- tent of 1.2% by weight were reacted with 31% by weight of water in a continuous reactor without addition of cata- lyst at a temperature of about 360 °C and a pressure of about 36 MPa (360 bars). The average reaction time was about 2 minutes. After cooling of the reaction mixture and separation of fat and water phases, the splitting de- gree was calculated to be 79.8%, which means that 79.8% of the total fatty acid amount of the fat is in a free form. Example 2wo 9707187 PCT/DK96/00353 10 10 100 parts by weight of the same fat as in example 1 were reacted with 31 parts by weight of water at a temperature of about 320 "C and a pressure of about 22.5 MPa (225 bars), and the catalyst sodium tetraborate containing 10 moles of water of crystallization was added in an mount of 1.0 g/l water, which corresponds to 0.0026 M. The splitting degree was calculated to be 79.3%. The average reaction time was about 2 minutes. As appears from the examples, relatively high splitting degrees may be achieved at very low reaction times. When the method is carried out in a number of steps, splitting degrees of about 99% may be achieved.wo 9707187 PCT/DK96/00353 10 15 20 25 30 35 1 1. A method for the splitting of fats and other esters by hydrolysis, characterized in that water is reacted with fat in a homogeneous phase at nearcriti- cal temperatures and supercritical pressures. 2. Amethod according to claim 1, character- ized in that the hydrolysis takes place at a tempera- ture in the range 300 to 500 °C and a pressure in the range 30 to 40 MPa (300 to 400 bars). 3. A method according to claim 2,character- ized in that the reaction proceeds for a period of between 0.01 second and 10 minutes. 4. A method according to claim1, character- ized in that the hydrolysis takes place in a liquid phase at a temperature in the range 350 to 370 C and a Pressure in the range 32 to 40 MPa (320 to 400 bars). 5. Amethod according to claim 4, character - ized in that the reaction proceeds for a period of between 0.02 second and 2 minutes. 6. A method according to claim1, character- ized in that the hydrolysis takes place in the pres- ence of a catalyst selected from the group consisting of salts of boric acid, silicic acid and phosphoric acid as well as silica or mixtures thereof. 7. A method according to claim 6, character- ized in that the salts of the acids are selected from salts of the metals in the first and second main groups.wo 9707187 PCT/DK96/00353, 10 15 20 12 8. A method according to claim 7, character- ized in that the salts of the acids are selected from sodium, potassium, magnesium and calcium salts. 9. A method according to claim 8, character- ized in that the catalyst is sodium tetraborate. 10, A method according to claims 6-9, charac - terized in that the hydrolysis takes place in liquid phase at a temperature in the range 250 to 370 °C and a pressure in the range 22.1 to 40 MPa (221 to 400 bars) with a concentration of the salts of about 0.1 M or less. 11. A method according to claims 6-9, charac - terized in that the hydrolysis takes place at a temperature in the range 300 to 320 "Cc and a pressure in the range 22.1 to 40 MPa (221 to 400 bars) with a concen- tration of the salts in the range from about 0.001 M to about 0.005 M. 12. A method according to claims 1-11, charac- terized in that the reactor is formed by the heat exchanger used for the heating of the reaction mixture.PCT/DK96/00353, WO 97107187 vw aseud aeg 493M BUTIEDATB a Tro 304 yonpozd Teo < burptou™ @ THO 304 4 i032 TS 7 uy (are | 1°311 INTERNATIONAL SEARCH REPORT Taternational application No. PCT/DK 96/00353 ‘A. CLASSIFICATION OF SUBJECT MATTER IPC6: C1IC 1/04 According fo Inerntional Patent Clasfaton (IPC) orto ath national casfiaton and IPC B. FIELDS SEARCHED ‘Minimum documentation searched (dassfcation sytem followed by IPC6: CLIC dasaieton eymboe) ‘Documentation searched other than minimum documentation tothe SE,DK,FI,NO classes as above vient that such documents are included i the Fads searched ‘Blearonic data bare consulted during the international earch (name WPI, FULLTEXT ‘of data base and, where practicable, each terme used) C_ DOCUMENTS CONSIDERED TO BE RELEVANT (19.08.80) Category*| Citation of document, with indication, where appropriate, ofthe relevant passages | Relevant to claim No. A DE 2120081 A (HECKMANWERK KG), 3 August 1972 1-12 (03.08.72) A US 4218386 A (TED J. LOGAN ET AL), 19 August 1980 1-12 Further documents ar listed in the continuation of Box: « See patent family annex ‘Swedish Patent Office Box 5055, S-102 42 STOCKHOLM Facsimile No. +46 8 666 02 86 7 pda ano dl ann 7 Sos nema SS CEEEE a= es Sore alee ee ee eames fing ew et fe an ih Se pape or teny steht ven “© siempre mae aga engl ee sit wri co Soares amc saaors pete decosmes une ar ssipaeeteane Vcomp rau ced oneen oe “0° demeanor el dens twin ee Scones seers se on Se ae acre as er ae “PY document published priae to the internatioal Ming date but later than ‘being obvious to a person skiled in the art mnt “te emma frome pt ay Das ofthe acl compladon of he aol sarah] Das of maling oe ists cach Fp 28 -11~ 1996 |.22 November 1996 sd maing addres oF The BAT Tatioraed ocr Dagnar Jérvman ‘Telephone No. +46 8 782 25 00 Ferm PCT/ISA/210(eecond sheet) (July 1992)INTERNATIONAL SEARCH REPORT Taternational application No. 28/10/96 | PCT/DK 96/0353 Information on patent family members Patent document Publintion Patent fay Pablzaion cited in Search report ‘ate rmembr(e) - 2120081 03/08/72 NONE 4218386 19/08/80 ran PCTTISA TAO (patent Tamly annex) ly O92}