BE499657A - - Google Patents

Description

       

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  IMPROVEMENTS WITH HYDROLYSIS OF DIACID, FATTY ESTERS.



   The present invention relates to the hydrolysis of fatty acid esters, more particularly the hydrolysis or fractionation of fatty oils or fats for the production of fatty acids and glycerin.



   For the purpose of making the following discussion clearer, hereafter, it will be preferred only to the latter materials cited, however, by the terms "fatty oil or" fat ", other acid esters should also be understood, and by" glycerin "other alkylated substances
The continuous hydrolysis or fractionation of these materials is usually carried out such that a mixture or emulsion of the oil or fat is subjected to high pressure and temperature while passing through a tank. - reaction - the products of the reaction - then passing through a separator so as to deposit the vapor and ensure, by the dispersion 'of the latent heat,

    The cooling and / or the partial concentration of the products Generally, the pressure is maintained at such a degree. that the water has the reaction temperature during the liquidated phase
In the hydrolysis of fatty oils or fats to obtain di-fatty acids and glycerin, said deposit causes cooling of the di-fatty acid product, and the partial concentration of 1-water to glycerin forming the. other produced but. the desirable high concentration of glycerin can only result from a subsequent and very expensive evaporation process.



   In the practical application of the aforesaid process it is generally intended to carry out the hydrolysis of more than 90% of the starting material, and to obtain the highest possible degree of concentration of water with glycerin in the starting material. the separator device, in order to save money in the subsequent vaporization phase.

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   For this purpose, the hydrolysis is generally carried out in columns comprising the usual plates ("bubble plates"), these columns being carried out
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 to operate under the high pressure required. 1; fatty oil or fat, with or without catalyst, and water being introduced in countercurrent into such a column, and the fatty acid being removed at the top of the column, for that the more or less highly concentrated glycerin is discharged at the foot of the column.



   However, it is essential to continue the concentration of glycerin. Installations of this kind are not economical for small operations, while in these installations it is also difficult to achieve the complete separation of the fatty acid phase and the fatty acid.
 EMI2.2
 aqueous phase of glycerin, because of the mutual solubility of the constituents at the reaction temperature.
One of the objects of the present invention is to provide a new process for the hydrolysis of fatty oils and fats (and other esters) and a new device for the non-execution of said process, which guarantee the achievement of this process.
 EMI2.3
 tion of a high degree of hydrolysis, the production of water with highly concentrated glycerin in the hydrolysis phase, and if desired,

   a very economical final subsequent concentration of water to glycerin For this purpose, the present invention
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 tion- refers to a process of hydrolysis of fatty oils and fats, characterized by the continuous passage of a mixture of starting fats and water through a reaction stage, - in which an amount of reagents corresponding to the production during a given period is- subjected to progressive hydrolysis
A certain amount of the mixture of fat and water (without catalyst) can be kept in the reaction stage for 1 1/2 to 3 hours;

   for example in a process designed for the treatment of one ton per hour the quantity maintained is of the order of three to six tons of reaction mixture o The optimum quantity may vary according to the nature of the quality of the ma -
 EMI2.5
 starting point, and / or 8tIit the degree of hydrolysis required, and it is expressly desired to reserve very broad limits concerning said quantity, to be determined experimentally.



   In any case, the quantity maintained in the reaction stage according to the process of the invention is clearly several times greater than the capacity of the hydrolysis reaction vessel according to the continuous hydrolysis processes with parallel streams practiced and recommended previously. .
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  The process according to the invention can be carried out without a catalyst, or with a catalyst mixed with the basic fat, such as for example a zinc oxide catalyst. In the latter eax, the. reaction time is considerably reduced compared to the aforementioned examples. The hydrolysis reaction may be accompanied by vigorous, continuous or
 EMI2.7
 intermittent In ... addition, the reaction can be accompanied - de- clm: t1f'f'9: ge, preférxbeg free-steam injection,., or, alternatively, indirectly by- eu1ation- d- * = - heated- fluid - o
The above-mentioned characteristic phase of the process according to the invention can be combined with:

  a phase of preheating the base mixture, the pro-
 EMI2.8
 products leaving the reaction stage at a temperature of the order of 250009 being capable of bringing the entering mixture to a temperature of at least 140 Co
Alternatively, - the reaction products can pass through the coil of an evaporator into which the glycerin water is reintroduced after the subsequent separation, the sensible heat of the products being used - to
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 concentrate the water to glycerin.

   In the latter case, - it is necessary to pre-heat the starting materials separately,
The present invention also relates to a process for the aforesaid hydrolysis, in which the mixture of base fat and water is passed continuously.
 EMI2.10
 naked, first through a reaction stage .., in ¯ p 'de- reactants,

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 EMI3.1
 corresponding to the feed for a fixed period is subjected to a gradual hydrolysis, the reaction products are subjected to a pressure release in a separation stage, the fatty acid separates mixed with hot fresh water is passed to through a second reaction stage
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 similar:

  ) the products of this second reaction are subjected to a pressure release and the separation of the fatty acid from the water with low concentration of glycerin, and the latter is used to circulate again oa '? water'? intended for the first reaction stage
Preferably, the fatty acid to be transferred from the first reaction stage to the second ext reaction stage, while it is subjected to reduction.
 EMI3.3
 tion of pressures, pa - 1 pump heated by the products of the first reaction stage pre @ ooing the separatioI1o
The products of the second reaction stage can be used to preheat the fresh fat and to reheat the diluted glycerin skin,

   both being directed to the first course of reaction, or, alterna-
 EMI3.4
 ti they- weigh- hearth used-for the evaporation of the- glycerin comas- exposed 0-1-derous.



   The present invention also relates to a reaction cellar for the execution of the aforesaid process which consists of a tank with a capacity for the quantities!? - de- mixed base-corresponding to the feed on a
 EMI3.5
 predetermined period, capable of withstanding considerable internal pressures presenting at or towards its opposite ends ducts for inlet and outlet, and compartmentalized by at least one internal wall which has an o- orifice for passage of the material> said orifice having a section "substantially equal to that of said conduits
Some or all of the compartments of the vessel may be provided with preferably rotary stirring means.

   
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  A preferred embodiment of such a reaction vessel.!) And two preferred embodiments of devices capable of carrying out the hydrolyzate process according to the invention are described below by way of non-limiting example only, with reference- to the accompanying drawings $, in which reaction; FIG. 1 sGhéma-tise in longitudinal radial CEHlpé a reaction vessel; FIG. 2 is a diagram of a single-stage hydrolysis device; FIG. 3 shows schematically a two-stage hydrolysis device.



  As shown in Figure 1, the cylindrical tank-1, having hemispherical ends 2-3, can be mounted vertically with the aid of the side supports 4. The tank 1-comprises a plurality of transverse partitions.
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 the 2Jr as well as a longitudinal agitator axis 6-which presents some or all of the compart1men-ts -. 2 agitator arms gag preferably of the axial or helical type. 2 orifices provided in the partitions 2. for the passage of the reactors =
 EMI3.8
 tîfsg thus which! a condW.t.d2> inlet .0 and an evacuation duct 11 are arranged.!)

   as shown successively in positions- substantially diametrically oppaeâes 9 so as to prevent -the formation of: 9 continuous channel. and d 9 will have in each compartment the content between the material and the agitator Alternately- and, for the same purposes, said- orifices can be distributed-around- 1 agitator-o The upper compartment 17 comprises, above the level of the inlet 08 a chamber z, gas 12 for 19accumulation of the gases given off during the reaction-, or-neutral gases introduced in order to maintain constant the pressure in- 1 cube- despite the possible variations of the- temperature- or- of the- vi-

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 tess for entering or leaving the materials Q La, tank 1 also comprises heating means,

   in the form of one or more coils 13 traversed by an Alterna- heating fluid
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 tively, the tank may have at least one nozzle9 duct or a similar element for 2 - 'free injection of steam o To promote the operation, some or all of the compartments of
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 reaction 7 are equipped with a thermometer 119 while a manometer 15 communicates with the gas chamber - 3.2 o Manholes 6 may also be provided in order to make the interior of the chamber accessible. tank for its maintenance and similar purposes.



   A hydrolysis reaction vessel as summarily described above is shown in Figure 2 applied in combination with auxiliary devices to carry out a one-stage hydrolysis process in conjunction.
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 8Ve-C form the method according to 19învention. Means for foUl: l! 1i:! R.- the reagents at the inlet 0 of the tank 1 comprise a feed water tank 21. and a fatty oil tank 22, arranged to introduce the materials in predetermined proportions in a mixer 23 comprising a stirrer 24.

   If necessary or desired, means (not shown?) For the adduction of a catalyst such as sine oxide in pulverulent form, to the mixer 23 or to the feed oil tank 22 which can then be used. It also has stirring elements. The mixer has a starting line which directs the mixed raw materials to the reaction vessel 1, via. a high pressure pump 25 and a heat exchanger 26.



    The agitator axis of the tank 1 is driven by an electric motor-34. The
 EMI4.4
 avaouation duct 11 of the tank 1 communicates with the heating coil z7, mounted in an evaporator 28 for the glycerin, so that the hot products passing through a separator vessel 29o contribute to the final eon- centration of glycerin., the water product a7 glycerin-from the hydrolysis reaction being returned to the evaporator through a pipe ¯0 starting from the bottom of said separator 29, and the fatty acid product being discharged at the top of the said separator 29 using a conduit 31.

   the concentrated glycerin is discharged from the evaporator 28 by means of a pipe 32, while the water vapor is discharged through an opening 33 communicating for example with a vacuum machine (not shown)
In such a single-stage installation according to FIG. 2, the hydrolysis or the fractionation of a fat can be carried out, by operating -
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 for example at a temperature of 190 order of 250 G and under pressure of approximately 35 to 40 a:

  'bay by obtaining a result of 90 to 92% of the starting fat, and using an amount of water of 60 to 70% based on the weight of said material If the proportion of water is increased to 'at approximately the weight of fat, hydrolysis can be done up to 93% or slightly more
The water and the fat, preheated in the heat exchanger 26 by an external heat source, are introduced at 10 into the heating tank.
 EMI4.6
 reaction i, and are optionally subjected "to a heating effect to adjust or maintain their temperature, with or without stirring,

   the evacuation duct 11 being closed during the operation of the mixing of the reagents and the products
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 until the tank is filled to the level known as conn1tit --- <the admittance: io-n 10 We then open the evacuation duct- n and the flow of materials continues to uniform speed.



   The materials passing through the tank 1 and passing from the inlet duct, through the compartments 7 (figure 1) to the exhaust duct 11, are released.
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 pressurized and t-eaperatuxe for a long time, and are preferably stirred iteratively so as to gradually achieve and continuously maintain the desired high degree of separation without difficulty. -y after cooling in the coil 27 of the glycerin evaporator 28, in the separator 29, in which the acid product

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 EMI5.1
 fat is separated from the water to glycerin, the latter returning to the evaporator.A By way of example,

     and particularly for the fractionation of a fatty oil or a fat for the production of di-fatty acid and glycerin, the vat
 EMI5.2
 1 designed, as said above, for a treatment of one ton per hour, must have a capacity of three to six tons of reaction mixture, \> cj) es-t = to = say a volume - d $ approximately four to eight cubic meters so that the material is maintained in the hydrolysis reaction zone for a period of approximately 1 1/2 to 3 hours.
 EMI5.3
 According to an alternative embodiment (instead of supplying the heat absorber 26 by an external heat source, and passing the products
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 reaction through a coil, such as 2 '' in an evaporator 28) the evaporator 28 can be heated externally,

   while a duct leaving from the outlet 11 of the tank 1 extends to 7. szxte side of the ehmgeo 26 and from there to the separator 29, the reheating of the fresh starting materials then being ensured by the products of reaction
The present invention also relates to an installation for the indicated purpose, comprising two tanks as described above, capable of carrying out a more complete hydrolysis in two stages, and each cooperating with one another.
 EMI5.5
 an individual separator, the discharge pipe of the first reaction vessel communicating with the associated separator a pipe incorporating a high pressure pump connecting the acid zone of the separator to the inlet of the second
 EMI5.6
 reaction vessel,

   the duct dl évwuation- of this second tank communicating with the second separator, and another enoope duct connecting the bottom or the zone of the glycerin solution of the aforesaid second separator to the duct of admission = mission of the first reaction tank. -
A. Such a two-stage plant may have corresponding varying means for the application of a heat effect to the reactants and for removing heat from the products.
Thus, for example, FIG. 3 shows schematically an installation in which the elements corresponding to those of FIG. 2 are indicated by the
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 same references o A heat exchanger 3 is arranged between the first reaction vessel 1 and its separator 29.

   One side of this de = ïer. represented by the coil 36, is used for the passage of 'products from the tank 1 to the separator
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 g2a The portion of non-hydrolyzed residual fatty acid-1-fatty acid or oil goes, at the- upper part of the separator 2 1, to a feed tank ¯49 via a Z pipe.

   then passes daae -m second mixer 3 where it is edited-in the presence -d9 = e7 ypqflée quantity of additional water, supplied by- 'on- tank d.s'eatr 2, and then passes to tr-obverse a duct 6 via a high-pressure pump g this portion thus returns to 1-other part of the heat exchanger 3p where it is reheated before entering the second tank 21 The relatively highly concentrated glycerin water from the lower part of the separator 29 is directed, via a pipe 47, to the glycol evaporator.
 EMI5.9
 cerine 280 In the. second tank of.

    In this case, the residual unhydrolyzed oil or fat reacts with the additional water under the temperature and pressure conditions obtained in said tank 51, and a very high degree of conversion to fatty acid is achieved. Reaction products of the tank
 EMI5.10
 51 pass, via line 1 & and coil 27 of the glycerin evaporator 9. ,, into the second separator 49, in which the fatty acid product is separated and then discharged through line 12.

   The glycerin em which is obviously can be concentrated (containing only the glycerin resulting from 1 9 hours or from the residual fat from the reaction vessel µ1} returns, by a pipe 22..9 the corresponding feed tank 21 with the first reaction tank ± 9 etc serves as a reaction teen for the first stage of hydrolysis.



   According to the modification of the installation shown diagrammatically in FIG. 3, it is possible to place between the second reaction vessel 51 and its corresponding separator.
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 respondent ¯ *, instead of a coil g a heat exchanger - whose two sides are used to pass respectively the products of the cuoe to said separator, and - 1 9 water with little glyaerinoe entering the bottom. du- separator an

 <Desc / Clms Page number 6>

 
 EMI6.1
 inlet duct of the first reaction vessel; thus, for example, the conduits 48 and 21 may comprise countercurrent sections inside such a heat exchanger.

   Alternatively such a heat exchanger
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 may be constituted by the exchanger 6 the conduit Ml connecting the tank .2! to the separator / fi, comprising Water instead of the coil 27} one side of said heat exchanger, the low-concentration--glycerin mixture discharged from the second separation chamber 49 via the conduit 53, and the oil or the fresh fat
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 directed from the mixer 2, towards the inlet of the first reaction vessel being thus preheated. In each of the last aforementioned modifications, 1-evaporation of the glycerin is provided by an external heat source.
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  In a two-stage above-mentioned plant, the hydrolysis being effect for example up to 92% to 93% in the first reaction vessel 1. the products are separated at 29 in relatively strong glycerine water which is directed to the water. medium evaporator and / or collector and a fatty substance incorporating approximately 7% to 8% fat or. unhydrolyzed oil.



  To complete hydrolysis up to 98% and above Danish second reaction vessel 51, it is necessary to remove approximately 5% or more of the content of
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 initial glycerin, ie about 0.5%, by weight of said incompletely hydrolyzed fatty substance. For this purpose it is possible to add a quantity of water, for example approximately 50% by weight of said fatty substance,
 EMI6.6
 by the feed tank Jg before the second reaction stage y to obtain therein approximately 1% glycerin water, which is, as described above, returned from the separator 49 to the feed tank 21 for.
 EMI6.7
 be retrieved as "em" for the first reaction stage.

   Increasing the proportion of water in the oil tends to raise the final degree of hydrolysis
If the first hydrolysis reaction is carried out at a temperature of the order of 250 C, the products can be cooled to approximately 90 C;

   in exchange of heat with the fatty substance and the supply of water passing from the mixer 43 to the second reaction vessel 51, this fatty substance enters the heat exchanger at approximately 8000 and exits therein.
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 proximatioem% 220 C Preheating the feed to the first reaction vessel
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 can be made up to the same level, when an exchanger such as 26 is provided in line 48, to follow the second reaction vessel, as mentioned above.



   By preheating the fresh feed in a one- or two-stage installation% and by reheating the fatty substance intermediately in a two-stage installation, it is only necessary to supply the reaction tank or tanks with sufficient heat to slightly increase the temperature. temple-
 EMI6.10
 rature of the input materials to the rebound temperature and to maintain this reaction temperature despite radiation and other losses.

   Thus the improvements according to the invention allow the application of a boiler or other extremely reduced heat source working continuously, at
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 instead of a large boiler or other heat source operating fu # rmittentt ?: It goes without saying that both the process and its means of
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 artwork may vary from the examples described above.



   The temperatures and quantities quoted can also vary according to wishes and necessities. In addition, the methods adopted for the adjustment and conservation of the temperature .. and the saving of calories may be modified according to practical considerations and the- oils- fatty-, fats or other esters to treat.

   Thus for example one-can use- heat exchangers -OR-devices for concentration- of-: the. glycerin as described, combined or not with heating or cooling means
 EMI6.13
 complementary paths, and the paths-and / or recirculations of the feed materials and / or the products can be modified in any way deemed suitable. In addition, in order to save caloriesS9- it is possible, at instead of a single effect glycerin evaporator obviously apply a multiple effect evaporator.,
The invention therefore discloses a process and a device for the hydrolysis or fractionation of fatty oils, fats or other esters,

   

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 EMI7.1
 extremely simple, economical9 and rational compared to known processes, both from the construction point of view and from the operational point of view, tone, and allowing to obtain the highest degree of hydrolysis desired or achievable, with a economic and rational subsequent recovery of gly-
 EMI7.2
 high concentration cerine
CLAIMS.



  1.- Continuous process for the hydrolysis of di-fatty acid esters, 9 parti-
 EMI7.3
 specifically the conversion of fatty oils and fats into glycerine acid and glycerin water, in which it consists in passing a mixture of starting material and dZ1e- - through a reaction stage, in which a quantity of said eootives9 corresponding to the diet during a period of


    

Claims (1)

period, is subjected to progressive hydrolysis 2.- Method according to claim 1, characterized in that a quantity of a mixture of starting fat and water without catalyst, cor- EMI7.4 corresponding to a feed of approximately 1 1/2 to 3 hours is maintained in a gradual hydrolysis reaction stage. ) 0 = Process according to claim 5L8 characterized in that an amount of a mixture of starting fat dJ1ew and a pulverulent catalyst corresponding to a feed of approximately 20 to 60 minutes is maintained in a stage. - hydrolysis reaction - poeogressivea 4. A method according to one and / or the other of claims 1 to 3, characterized in that the hot products leaving the reaction stage are used to heat the mixture of fat and incoming water. EMI7.5 5 om A method according to 1-'a.te and / or I9 a.te- claims 1 to 3, characterized in that the hot products leaving the reaction stage provide the heat necessary for evaporation of the l water to glycerin, before the separation of 1-1 gr-.e acid and Pem to glycerin. 60- Process according to claim 1, characterized in that the reaction products pass through a separation stage, the separated fatty acid mixed with fresh water pass through a second -similar- - reaction stage, the products- of- this second reaction- being subjected to the separation of 19-fatty acid- from water with weak glycerin, the latter being recovered to circulate EMI7.6 z, new as- pU1J- for the- first stage of. ReactioR- <J zoom Process according to claim 6, characterized in that 1 fatty acid transferred from the first separation stage to the second reaction stage; , EMI7.7 operation during which it is subjected to an increase- of pressure for- example- by a- pump is reheated by] .S1é (] - heat hange-with- the-products of the first stage de- ration! 1 preceding the separatioITo 80- The method of claim 6 or 7, characterized in that the hot products of the second reaction stage are used to preheat EMI7.8 the fat- fresh and for reahaaffet-een with dilute glycerin both directed to the first reaction tank 9. A method according to claim 6 or 7, characterized in that the hot products of the second reaction stage are, before the. separation from EMI7.9 fatty acid and glycerin em which are used to effect or promote the development of said glycerin water 10.- Reaction vessel for non-execution of the process according to 1-moon and / or EMI7.10 .9a.te of the preceding claims, characterized in that q-a9elle consists of a reservoir with a capacity for mixing quantities of bMe - 9 oornzpcn- dmt k 1 * elbnentation over a predetermined period-, capable of ergslater with considerable internal pressures, presenting at or towards opposite ends of the so-called arlmfmon- and awakening ducts, and compartmentalized by at least one internal wall which has an orifice for the passage of material, said orifice having a section substantially equal to that of said crondu-its0 11. Reaction vessel according to claim 10, characterized in EMI7.11 that some or all of the compartments include stirring means <Desc / Clms Page number 8> preferably rotary so 12. A reaction vessel according to claim 10, characterized in that it is cylindrical, has hemispherical ends, is designed so that its axis is disposed vertically; and comprises one or more transverse partitions and an axially extending rotary agitator shaft, said shaft being, in some or all of the compartments. fitted with stirring means preferably of the axial or helical type. 130- reaction vessel according to claim 12, characterized in that the orifices of the partition (s) and the inlet and outlet ducts EMI8.1 evacuation are arranged- SI: 1eees-s.ivement in substantially diametrically opposed positions-s-, where said orifices- are distributed around an agitator axis, so as to prevent the formation of a continuous channel and d 'ensure, in each compartment; ,, the contact between the material and the agitator. 14. A reaction vessel according to claims 10 to 13, charac- terized in that it has in - or in communication with - its upper part. EMI8.2 inside a gas chamber for the cati # r of the gases, released during the reaction or introduction to maintain constant the internal pressure of the tank, despite any variations in temperature or inlet speed or - material exit 15.- Installation comprising a reaction vessel according to claims 10 to 14, characterized in that said vessel is combined with a heat exchanger a conduit on one side of the heat exchanger serving EMI8.3 to 19addo maintance of a fresh reaction mixture to the c8admissror pipe of the tank, and a deahatgo duct from the vessel leading to the other side of the heat exchanger, the reaction products thereby imparting a heat effect to the fresh starting materials. 16.- Installation comprising a reaction vessel according to claims 10 to 14, characterized in that said reaction vessel is combined EMI8.4 with means for evaporating the glycerin the discharge duct of the tank communicating with a heating coil of said evaporating means, so that the hot products, being directed to a separator, contribute to the final concentration of glycerin. 17.- Installation comprising two reaction vessels according to claims 10 to 14, characterized in that the discharge pipe of the first reaction vessel communicates with an individual separator, a pipe, EMI8.5 incorporatit-a high pressure pump connecting the aside zone of said separator to the inlet of the second reaction tank, the discharge duct of this second tank communicating with the second separator-, and yet another duct connecting the bottom or the zone of the glycerin solution of said second separator EMI8.6 to the deachissioil line of the first reaction tank-o 180- Installation according to claim 17, characterized in that between the first reaction vessel and its separator is disposed a heat exchanger, whose two sides are used for the passage, respectively EMI8.7 products from the tank to the separator, and fatty acid- - mc-orporaniï-the buUe or residual fat - not hydrolyzed-- - pre-cleaning in the presence of an appropriate amount of water, from the separator to the second tank of the reaction 190- Installation according to claim 17 or 18, characterized in that between the second reaction tank and its associated separator is disposed an exchanger whose two sides serve for the passage, respectively, of the products from the tank to said separator, and low glycerin water discharged at the bottom of said separator - with or without addition of fat or fresh oil EMI8.8 - to the intake duct of the first reaction tank 20.- Installation according to claim 17 or 18, characterized in that between the second reaction vessel and its associated separator is dis- EMI8.9 placed a heat exchanger coil placed- 1-inside- the glycerin evaporator device., the heat of the products of the second reaction tank being recovered in the glycerin concentration process <Desc / Clms Page number 9> 21. Improvements in the hydrolysis of fatty acid esters, substantially as described and illustrated.