DD228805A1 - APPARATUS ARRANGEMENT FOR OBTAINING GLYCERINE HIGH PURITY FROM HIGH PRESSURE PALE PRODUCTS - Google Patents

Abstract

The invention relates to an apparatus circuit for the production of glycerol from high pressure cracking products. The invention has for its object to act with an apparatus circuit on the Vorreinigungs-, deposition, evaporation, distillation process so that at greatly reduced material, energy, chemicals and labor force effort each gap mixture at max. Yield of glycerol can be worked up. According to the invention, the object is achieved with an arrangement of evaporators, separating vessel and distillation / rectification column, as well as agitators and ion exchangers, which are linked to one another in a specific manner.

Description

Title of the invention

Apparatus arrangement for obtaining high purity glycerine from high pressure cracking products

Field of application of the invention

The invention relates to an apparatus arrangement, in particular for the production of high-purity and pharmaceutical glycerol (saponified glycerol) from fats of plant or animal origin, which have been subjected to high-pressure cleavage _o

In addition, the invention can be applied where fats have been cleaved by lyes (leached glycerine), as far as prior to the actual work-up according to the invention, for example after a preliminary evaporation, the salts present in this crude product (about 10% to 10% by weight) 30%) were separated and completely removed,

Characteristic of the known technical solutions

By splitting fats of vegetable and animal origin with water, a glycerine water (saponified glycerine water) is obtained whose glycerol content is between 6 and 15%, depending on the splitting method. It is customary to subject the glycerine water to a pre-purification. (Osterroth, D., yearbook for the practitioner, publishing house for iron, industry, H, Ziolkowski K.G, Augsburg 1966 S, 32). At the hydro-

-13 9.84-01

On the other hand, glycerine water may still contain fatty acid moieties as well as other light and high-boiling impurities. * For the above reasons, glycerine waters, eg using baryta-hydrate, may be present (Aetzbaryt), sulfuric alumina and aluminum sulfate are treated in special apparatus and filtered. Prior to this chemical treatment, it is customary to versetzest the Glyzerinwasser z _e as sulfuric acid to a rapid separation of the phases to allow fatty acid and Glyzerinwasser ". Further processing is carried out by thermal or ion-exchange processes. If the glycerol is obtained by distillation, this plant is preceded by an evaporation plant; if it is purified by means of an ion exchanger, it is treated. Apparatus downstream of a Sindampfunganlage.

For me, this process of escaping is usually accompanied by three-stage columns connected in series. I circulation circulation evaporator era and for residual evaporation a IXinnschichtverdampfer used. For distillative removal of the low-boiling components (amines and others), a rectification column which is operated with reflux at about 1333 Pa is used. The chemical pretreatment of the crude glycerin waters separates the fatty acids as undistillable alkali metal salts in the bottom. The freed from the precursor mixture is then subjected in a stripping column to a main distillation at about 700 Pa, here 80-85 % of the glycerol contained in the thickened crude product incurred * In a downstream stripping column at about the same pressure, the glycerol except for a Glyzerinpech to about S. 10 % distilled off _o This second distillate is again a. Second Durchsang in the

subjected to first main evaporation. (Stage, EL DE 1 079 257, 1960)

In the distillation, the addition of sodium hydroxide solution and steam is provided and followed by filtration to improve the color numbers with carbon. "With this procedure and concatenation of appropriate apparatus, an end product, at least the main length, with about 85%, as a drug glycerin (DAB VI product) should be obtained.

Another possibility to work up the glycerine water is given by ion exchangers. (J.Amer.Oil Chemists Soc., 29, 1952, pp. 318-320). The economy of workup with ion exchangers is in the processing of glycerol from fats and from residues of the distillation of bad carcasses, eg lard material, as a result of the then too high exposure of the ion exchanger in embossed (Gianozza, A., La Rivista Italiana delle substance brasse, Vol. XL IV, 1967, 8471-474). The large amounts of waste water which are produced during washing and regenerating the ion exchanger must be neriert, beschr än ken when using the above poor raw materials, the application possibilities of the especially when discoloration saustauscher that .- "because of its low sorption capacity often rege- ^%." ion exchange process. (T'erelak, et al. Chem. Technique 33, 1931, Ξ. Δ 3. 315-316). When working with ion exchangers, the glycerol water is fed to a downstream two-stage filter system (eg Wofatit 3A 60) after the phase separation mentioned at the beginning. For inoculation, a certain amount of sulfuric acid is added via metering devices. At this stage deodorising and decolorization takes place "Thereafter, the glycerine water passes through a heat exchanger into an associated Eeißfällrührmaschine" Here is done at about 100 ° G a Hachfällung with some lime,

so as to avoid an excessively high load on the desalination filter »The turbidity cools in the interposed heat exchanger to about 70 ° G. It is carried on a Zentrifugalscheibendruckfilter and then the liltrat is cooled by heat exchanger to about 30 ⁰ G and then a two-stage coarse desalination (eg · Wofatit KPS, AD 41) and then a two-stage l'desalting (eg Wofatit EPS, SPK) subjected. Thereafter, the multistage lindampfung described above takes place in columns with natural circulation evaporate and the Hasteindampfung in a thin film evaporator.

 The energy requirement for a ton of pure jelly from a 10% glycerine water solution is for the

6 · evaporation system about 5 * 10 W and for the operation of the ion exchanger about 0.04. 10 W. The degree of efficiency due to crusting phenomena on the heating surfaces is severely restricted as a result of the "solids" present *

The expenditure on equipment is very high due to the chemical treatment and frequent heating and cooling processes. «

Object of the invention

The aim of the invention is to reduce the energy and equipment expense.

Explanation of the essence of the invention

- Problem of the invention -

The object of the invention is to make it possible with a Apparatean Regulation distillative recovery of high purity glycerol energieökonoiaisch and with minimal appa tive effort.

- essence of the invention -

According to the invention, this object is achieved in that a device arrangement of a first falling film countercurrent evaporator for the constriction, a condenser, a vessel for phase separation, an udder, a second and a third falling film countercurrent evaporator as two-stage evaporation and as Sohglyzerinverdampfung a fourth falling film Countercurrent evaporator arranged underneath Haturumlaufverdampfer and the apparatuses are liquid product side connected in series, the process for Hestrückstand the Haturumlaufverdampfer has a branch as circulation line for heavy product, which is connected to the separation vessel to the liquid product line * At the head of the first falling film countercurrent evaporator is the Hohproduktleitung connected. The phase separation vessel has an upper course for the fatty acid as a light phase, which is discharged. The Pallfilm countercurrent evaporator for the Rohglyzerineindampfung product vapor side downstream of a distillation / Eektifikationskolonne is removed from the overhead as a low-boiling components of the flow and therefore connected to a condenser _A _Am_Sumpf-the-2es tiilier- / Sektifizierkolonne the finished product line is arranged which expediently a Torlagbehälter can be interposed and a cooler for cooling the finished product (dynamite glycerine) - to about 30 ⁰ C · The Fallf ilm Gegenstroinverdampf he is narrowing expediently on the steam side connected to the falling film Geganstromverdampfer the second Sindampfungsstufe, so that the steam from the constriction can serve as a heating medium for the second Eindeinpfung and is then discharged via a distillate line and a safety cooler below. The product vapor (water vapor) from the first and second evaporation stage is on the

removed the heads of the evaporator arranged steam lines.

Eeizmedienseitig the first falling-film countercurrent evaporator, he expediently downstream of the second PaIIfilm countercurrent evaporator, with a decompression valve is interposed.

Should drug glycerin or glycerin high. Purity, the distillation / rectification column is followed by the liquid product side or the receiver with a water supply followed by a cation exchanger and an anion exchanger or a carbon filter. The anion exchanger or carbon filter is provided with a low-temperature sintering step.

, Falling film countercurrent evaporator connected. In this palle, the iallfilm countercurrent evaporator is expediently connected downstream of your 5-fold countercurrent evaporator to the first step of the first step The cooled product is likewise cooled and removed in the cooler 'Ettsäure-Glyzerinwassergemisch in the first falling film countercurrent evaporator is concentrated to about 55 "to 50% glycerol concentration and here under rectification conditions small amounts of low-boiling acid components removed with the cracked water vapor and fed as a heating medium the third falling film countercurrent evaporator * The effluent product is in the cooler cooled to about 80 ⁰ C and fed to the J'ettsäureabscheidebehälter, wherein the continuous deposition of.Fettsäure as a light phase at a residence time of about 15 minutes. The glycerin water is drawn off at the bottom and filtered in the filter, followed by residual drainage in the two successive falling-film countercurrent evaporators.

The degree of glycerol losses during evaporation is determined by the steam velocity in the last step. It should not exceed 10 m / s, preferably 5 m / s effective steam velocity. Under these conditions, the amount of glycerol passing from this last stage with fission water vapor is -5. 1% · Based on the glycerin content in the starting mixture ί 0.2%

The concentrated to> 99 % crude glycerol is subjected in the interposed Pallfilm Gegenstrom- and Naturuffllaufverdampfern a known rectification with stripping section such that a main and residual evaporation takes place together at about 400 Pa ,, the high-boiling fractions arrive rectifying "in the residual residue, which is partially discharged via the drain line and partially recycled via the circulation line before the filter back to the process »The Glyzerindampf is fed to the rectification, in which the volatile constituents rectified under a pressure von'etwa 133 Pa and after condensation in the condenser separately be discharged.

The entire run-off and residue-free distillate runs down and is recorded in the original.

25, trapped, cooled in the cooler and discharged, In the work-up as pharmaceutical glycerine, the distillate from the rectification is diluted with deionized water in the stirred tank to about 50 % , then the cation exchanger and following the anion exchanger and then a final dewatering stage in Eallf ilm Gegenstromverdanipf he operated at the most with a vapor velocity of 10 m / s and under a distillation pressure of 19j9 kPa. The ion exchangers are regenerated with small amounts of sodium hydroxide solution and hydrochloric acid,

If high purity glycerol is to be obtained from inferior product, the liquid product from the distilling zone will direct your stirred tank, there with. the five-fold amount of deionized diluted in water, the carbon filter and then fed to the Pallfilm- countercurrent evaporator for evaporation,

embodiment

The invention will be explained in more detail below using an example,

FIG. 1 shows a schematic representation of the apparatus according to the invention for producing highly pure or pharmaceutical glycerin.

From a glycerol water with a Glyzeringehalt of 8.4 % and the chemical "" parameters pH 4.06, acid number 0.27 and iodine color number 6, as obtained in the high pressure cleavage of rapeseed oil-Eaffinationsrückstand, by means of the inventive apparatus circuit. Pharmaceutical grade glycerin and at a concentration of 88 % .

The cracked water F1 is fed with 1GO ⁰ C at the head of the first falling film countercurrent evaporator 1, which is heated with water vapor preferably 0.51 MPa from line W1 · evaporate from the mixture at atmospheric pressure. 84% dissociation water at 100 ⁰ O, which is withdrawn via line Da1 at the top and fed as a heating medium to the third evaporator 7 above. The below the evaporator 1 narrowed 'mixture is fed via line P2 the cooler and cooled to 80 ⁰ G and passes on to the Phasentrenngefä £ 3 x takes place here as' a residence time of Produktgeirisches of about 15 minutes, the continuous deposition of the fatty acids as the upper phase, which flows via ^: line F3 and that of glycerin x1 as the lower phase.

The glycerine water with the characteristic values: pH value 4.2, iodine color number 166, acid number 2.04, ester count 5j3 is added via line x1 and udder 4 to the first lindening stage of the falling film countercurrent evaporator 6 at the top. »Here, the defoaming takes place at about 19 In this first evaporation stage 6, a further 10% of splitting water are distilled off at 60 ° C. and removed via line Da 2, and the unevaporated portion reaches the top at about 125 ° C. via line x 2. second evaporation stage 7. This counterflow film evaporation is likewise operated at 19.9 kPa. Here, the test is carried out at an effective vapor velocity of about 5 m / s. 3s accumulate approximately 6 % Sp .altwasser that via line

The Eohglyzerin with a temperature of 100 ⁰ O passes therefore over line x3 to the Pallfilm Gegenstromverdampfung 9j which with steam of the pressure stage 1,2 SiPa is operated · The The residue accumulating here is recycled in an amount of about 4 % via line R1 in the process before the filter and discharged in an amount of about 1 % as residual residue via line R2 · the Glyzerindampf is the distillation / Eektif ikationskolonne 11 is fed below having a flow amount of 0.5% across capacitor 1Ϊ and line VRI is taken at Ecpf from the vapor mixture, the effluent from the column 11 sump product with a temperature of about 130 ⁰ O is fed via line x5 ^ en agitator 15. After addition of equal portions of deionized water, the water-containing glycerine mixture is subjected to a fine cleaning in a cation exchanger 17 and then in an anion exchanger 18. Thereafter, the purified glycerol water

in the iallfilm countercurrent evaporator 16, in which it passes via line x6, at an effective steam velocity of 5 m / s, to 88%, to the concentrated outlet, which becomes vapor at a pressure of 19-9 Pa Pa and 6C ⁰ C. discharged *

The narrowed to 88% end product passes via line 27 into the cooler 14 and is discharged with about 30O ⁰ G.

 The final product is a glycerol concentrate with the chemical. Characteristicsί pH 6.2, acid number 0.02, nitrogen number 0, iodine color number <1. Sulfide chloride heavy metal ions as well as reducing impurities. unavailable. For one liter of pharmaceutical glycerin, with: a yield> 99% based on glycerol content

  15% f & water and based on an 8.4% glycerine water solution are required;

Sodium hydroxide solution 1 kg, hydrochloric acid 0.2 kg, deionized water 1.4 mr, of energy for evaporation 4.9 "10 ⁰ W, for distillation / Hektifikation 0.3 · 10%" and wastewater

  3 3

0.5 ^ - slightly acidic, 9 »5 egg with a glycerine concentration of ^ 0.06%, 9» 7 21 from the acidification 1 with an acidity f. 20 ppm.

List of reference items

F1 fissured water pipe

F2 line for concentrated glycerine water

F3 line for fatty acid

W1 heating medium line

W2 connection extender evaporator 6/16

R1 circulation line

k1 heating medium connection pipe evaporator 1/6

x1 glycerine water line

x2 glycerin water from the 1st stage of desalination

x3 raw glycerine line

x4 line for backlog

~ <S3 Eroduktleitung

x6 pure glycerine water pipe

x7 finished product line

, VI ........ drain line for flow

Da1 split steam line '

The fission steam vapor line from the first stage of leaching

.'Da3 fissured water drainage line from the 2nd stage of vaccination

LI Brüdenleitung the Sindampfungsanlage

L2 ventilation line

L3 to L6 condensate lines

I Falling Film Counterflow Thinner for Sinking (Sinenger) © 2 Cooler

3 phase separation vessel

4 filters

5 relaxation valve

6 second falling film countercurrent evaporator (1st stage of desulphurisation)

7 third falling film countercurrent verdipfer (2 * Sindainpfungsstuf e)

8 safety coolers

* 9 falling film countercurrent evaporator 10 STat uruml hey steam he

II Distillation ZRektifikationskolonne

12 capacitor

13 product template

19 as4-0-1988ss

15 stirred tank with Bührer

16 falling film counterstron / earth dill

17 cation exchangers

18 anion exchanger

19 Eezipient

20 carbon filters

21 De-ionised water line L7 supply - Krexsia supply

L8 distillate circulation line drain line

19.9.84-01 98889

Claims (6)

claims 1. An apparatus arrangement for obtaining high purity glycerine from high pressure cracking products, consisting of ITallfilm Gegenstromverdanipf ern, ua door recirculation damper, rectification column, coolers, phase separation vessel and! Filter, characterized in that in the flow direction of the "product, a first falling film countercurrent evaporator (1 ) with condenser (2) as a diffuser, a vapor separation vessel (3) with an upper discharge line (5 * 3) and this a second and third Jaiss * \ film countercurrent evaporator (6, 7) as a two-stage Ein evaporation, which in turn a fourth falling film countercurrent evaporator (9) and the natural circulation evaporator (10) as the product main and residual evaporator. is downstream and the product main evaporator (9) product steam side, the distillation / rectification (11) is downstream, which at the sump a finished product line (x5) and at the top of the capacitor (12) a drain line (Y1) for the flow up 'and the residue line (x4) of Hestverdampf ers (10) via the circulation line (R1) with the Glyzerinwasserleitung (xi) in front of the! Tilter (4) and the drain line (R2) is connected. 2. Apparatus arrangement according to claim 1, characterized in that the process steam side of the Einengers (1) the Heizinedienseite the second evaporation stage (7) via a steam line (Da1) is arranged downstream * 3 «apparatus arrangement according to claim 1 and 2, characterized in that the heating medium side of the 3inenger (1) the first Mndampfungsstufe (δ) via a heating medium line (ki) and an expansion valve (5) is arranged downstream. 4 · Apparatus arrangement according to claim 1 to 3, characterized in that the distilling ZHektifizierkolonne (11), on the product side a conventional stirring. container (15) with fresh water supply (21), a known cation exchanger (17) _} a per se known Α / ni onenaustauscher (18) and a lallfilm countercurrent evaporator (16) whose liquid product line (x7) the finished product line and. whose. Steam line (Da5) is the waste line, downstream 5 · Apparatus arrangement according to claim 1 to 4, characterized by ,, that the. Eührbehälter (15). on .' conventional eole filter (20) and the carbon filter (20) 'of the falling film Gegenstronrverdampfer (16) is arranged downstream 6. Apparatus arrangement according to claim 1 to 5> characterized in that the Yerdampfer (6) of the first evaporation stage of the falling film countercurrent evaporator (16) is arranged downstream via Heizmedienleitung (W2) · - For this a sheet drawing