CN106977374A - The method that supercritical carbon dioxide extracting separates alkoxide mixt - Google Patents
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- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
- C07C29/84—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by extractive distillation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention provides the method that supercritical carbon dioxide extracting separates alkoxide mixt：A) supercritical carbon dioxide is passed through in extractor, one-level knockout drum is transferred to after being extracted to the polyalcohol in alkoxide mixt；B) supercriticality that temperature and pressure still keeps carbon dioxide is reduced in one-level knockout drum, the polyalcohol for being extracted out is separated from carbon dioxide, and the second-order separation tank is admitted to dissolved with the supercritical carbon dioxide of a small amount of polyalcohol；C) it is previously added defoamer in the second-order separation tank, decompression makes carbon dioxide be changed into common gaseous state from supercriticality, further separating multicomponent alcohol, realizes being kept completely separate for polyalcohol in alkoxide mixt.
Description
Technical field
The present invention relates to the method that supercritical carbon dioxide extracting separates alkoxide mixt, and in particular to uses overcritical two
Carbonoxide realizes the method that polyalcohol is separated with acylate, belongs to biopolyol production technical field.
Background technology
Bioenergy is the reproducible energy on the earth, and sugar, glycitols compound can provide the biological energy depended on for existence
Amount, and the source of this class material is mostly plant, such as starch.Pass through the materials, Ke Yijin such as initial stage, the starch of most original
The multistep reactions such as water-filling solution prepare glucose, xylose, sucrose, maltose, fructose, sorbierite, xylitol, mannitol, different sorb
Common feature in alcohol etc., these sugar alcohol structures is the carbon atom with more than five, and has the hydroxyl of more than four, this
Class material can often be used as food or food additives.
However as the gradually atrophy of non-renewable petroleum resources, and because glycitols material has polyhydroxy structure
A variety of polyalcohols can be cracked under conditions of high-temperature and high-pressure hydrogenation, therefore this biolobic material energy is little by little participated in
It is converted into the ranks of chemical products.As Changchun great achievement biochemical technology group is disclosed in alkaline water in CN200510008652.0
After solution is hydrogenated with conditions of existing by Raney's nickel series catalysts, sorbierite can be cracked into ethylene glycol, propane diols, 2,3- fourths
The materials such as glycol, 1,2- butanediols, BDO, glycerine, lactic acid, acetic acid, formic acid, wherein organic acid and the alkali in system
Reaction generates acylate.United States Patent (USP) US4366332A also discloses that sorbierite hydrocracking can generate a variety of polyalcohols
And acylate.
From the point of view of above-mentioned prior art, after the hydrogenated cracking of glycitols material, alcohol and acylate are generated, by reaction solution
By dehydration, after dealcoholysis, remaining substantial amounts of acylate, glycerine, a part of dihydric alcohol and dehydration polyalcohol in mixture
Ether etc..But in actual separation experimentation, because the content of acylate in alkoxide mixt is excessive, reach about
Between 20-30wt%, and be dissolved in polyalcohol, therefore, alkoxide mixt occur dark brown, it is sticky, easily solidify, solidify after become
It is hard and the problem of be difficult to melt again, the yield of main polyol product is not only have impact on, selection, the separation of separation equipment is returned
The design of technique brings very big difficulty.
Donghua University Shao Xiao clumps in its Master's thesis《Application of the heavy constituent in degradation plastic in corn chemical alcohol industry
Exploitation》In discuss negative effect of the acylate to technique in alkoxide mixt in detail, therefore, how from alkoxide mixt
Middle remove acylate extracts more pure polyalcohols, an important research direction as the field.
It is by adding in alkoxide mixt thing that the method introduced in polyalcohol, most literature is extracted from alkoxide mixt
Enter a certain amount of water or after low-carbon alcohols are dissolved, be acidified with the concentrated sulfuric acid, generation sodium sulphate or niter cake, salt can be tied
The form of crystal is separated out, after crystal is filtered, and is decolourized with some oxidants, is further removed organic acid, mixing has just been made many
First alcohol.This polyols blend can be for materials such as synthesizing polyester, unsaturated polyester resins, or is returned directly to rectifying column
In, further separate various polyalcohols.But this method step of preparation process is very long, unit trivial operations, polyalcohol with it is organic
Azeotropic can also occur for acid, and separative efficiency is relatively low, and separation is difficult, and organic acid has corrosion to equipment.
It is, thus, sought for a kind of new method for removing acylate in alkoxide mixt, realizes to separate and simultaneously extracts alcohol
The purpose of polyalcohol in salt.
The content of the invention
It is an object of the invention to provide the method that supercritical carbon dioxide extracting separates alkoxide mixt, by overcritical
Polyalcohol in carbon dioxide abstraction alkoxide, using multi-stage separation technique, and in separating technology with the use of defoamer so as to
Realize being kept completely separate for polyalcohol in alkoxide mixt.
In order to realize above goal of the invention, the technical solution adopted by the present invention is as follows：
The method that supercritical carbon dioxide extracting separates alkoxide mixt, is comprised the steps of：
A) alkoxide mixt is added in extractor, by extractor it is closed after, be passed through supercritical carbon dioxide, it is mixed to alkoxide
Polyalcohol in compound is extracted, and the supercritical carbon dioxide for being dissolved with polyalcohol is transferred into one-level knockout drum；
B) keep the pressure and temperature in one-level knockout drum to be less than extractor, but still keep the supercritical state of carbon dioxide
State, the polyalcohol for being extracted out is separated from carbon dioxide, after standing separation, through separating dissolved with a small amount of polynary
The supercritical carbon dioxide of alcohol is admitted to the second-order separation tank；
C) add defoamer in advance in the second-order separation tank, by convey in one-level knockout drum come dissolved with a small amount of polyalcohol
Supercritical carbon dioxide gas is depressured, and carbon dioxide is changed into from supercriticality after common gaseous state, standing separation, dissolved with
Polyalcohol in the supercritical carbon dioxide of a small amount of polyalcohol is separated positioned at the bottom of the second-order separation tank, is changed into gaseous two
Carbonoxide enters gas concentration unit.
In step a) of the present invention, the source of the alkoxide mixt is that the multi-sugar alcohol hydrogenation that carbon number is 6 to 12 splits
Solve liquid rectifying after alkoxide mixt, the carbon number for 6 to 12 multi-sugar alcohol include but is not limited to glucose, fructose,
One or more in maltose, sorbierite, mannitol and xylitol etc..
In the present invention, the gross mass based on alkoxide mixt, the alkoxide mixt includes following components：
Dihydric alcohol 55-75wt%, the dihydric alcohol includes but is not limited to ethylene glycol, 1,2-PD, 2,3-butanediol, 1,
One or more in 2- butanediols and 1,4- butanediols etc.；
Acylate 20-30wt%, the acylate includes but is not limited in formates, lactate and acetate etc.
It is one or more；
Other materials 5-15wt%, including but not limited to degree of functionality are more than 2 polyalcohol and its dehydration product, such as the third three
One or more in alcohol, anhydrous sorbitol, dehydration xylitol and glycidol ether etc..
Polyalcohol in present invention alkoxide mixt described here includes the polyalcohol of dihydric alcohol and degree of functionality more than 2
And its dehydration product.
In the present invention, in step a) extractors, the pressure (gauge pressure, similarly hereinafter) of described supercritical carbon dioxide is 10-
25MPa, preferably 12-18MPa；Temperature is 60-180 DEG C, preferably 120-160 DEG C.
In step a), the extraction time is 3-12 hours, preferably 5-8 hours.
It is dissolved with the supercritical carbon dioxide of polyalcohol in step a) to be transferred to after one-level knockout drum, wherein overcritical titanium dioxide
The polyalcohol that carbon is extracted accounts for more than the 90wt% of polyol quality in alkoxide mixt, preferably more than 95wt%, more preferably
More than 97wt%, is analyzed using liquid chromatograph；Extractor takes out remaining alkoxide mixing after being down to normal temperature and pressure
Thing, directly as fixed-end forces.
In step b) one-level knockout drum, the supercritical carbon dioxide pressure is 8-15MPa, preferably 9-12MPa；Temperature
For 40-80 DEG C, preferably 50-70 DEG C；The time of the standing separation is 1-4 hours, preferably 2-3 hours.
The polyalcohol for being extracted out in step b) is separated from carbon dioxide, after standing separation, and polyalcohol is located at
The bottom of one-level knockout drum, is located at tank top dissolved with the supercritical carbon dioxide of a small amount of polyalcohol.
After step b) polyalcohols are separated from carbon dioxide, the polyalcohol dissolved in supercritical carbon dioxide is carried out
Sampling analysis, is analyzed with liquid chromatograph, and the content of polyalcohol is below 10wt%, preferably below 5wt%, more preferably
Less than 3%, the gross mass of the polyalcohol gone out based on supercritical carbon dioxide extracting in step a).
In step c) the second-order separation tank, the pressure carbon dioxide is 0-7MPa, preferably 3-5MPa；Temperature is 40-80
DEG C, preferably 45-60 DEG C；The described standing separation time is 5-10 hours, preferably 6-8 hours.
In step c), the quality of the defoamer of the addition is the 0.5-2wt% of alkoxide mixt gross mass in step a),
It is preferred that 0.7-1wt%；The defoamer is selected from alcohol ethers defoamer, including but not limited to polyoxyethylene polyoxypropylene pentaerythrite
One or more in ether, polypropylene glycerol aether and polyoxyethylene polyoxypropylene glycerin ether etc..
In step c) after standing separation, position is separated dissolved with the polyalcohol in the supercritical carbon dioxide of a small amount of polyalcohol
In the bottom of the second-order separation tank.
In step c), it is changed into gaseous carbon dioxide and enters gas concentration unit, wherein contains micro polynary alcohol, polyalcohol
Volumetric concentration be not higher than 1500ppm, preferably no greater than 1000ppm, gaseous carbon dioxide stores repeatable profit after purification
With.
Present invention additionally comprises step：
D) polyalcohol for isolating one-level knockout drum and the second-order separation tank bottom divides by post processing such as distillation operation
Various polyol products are not obtained.
Beneficial effects of the present invention are as follows：
1st, supercritical carbon dioxide extracting the second-order separation technology is passed through, it is to avoid superfluous using acidifying, filtering, de- low-carbon alcohols etc.
Long unit operation；The irretrievable problem of polyalcohol in sticky alkoxide mixt is solved, while solving environmental protection, the three wastes
The problem of.
2nd, by adding defoamer in the separation process of the second level so that polyalcohol can be complete in the separation process of the second level
Portion is separated from alkoxide, is solved and is seriously foamed during sticky polyalcohol and carbon dioxide separation, overflows what tank was caused
Loss of material.
3rd, by controlling the temperature and pressure of the second-order separation respectively, taking off completely for acylate in alkoxide mixt is realized
Remove, and realize the high efficiency separation of wherein whole polyalcohols, improve the total recovery of polyalcohol.
Embodiment
The content of polyalcohol in carbon dioxide is analyzed using liquid chromatograph, mobile phase is that pH is 2-3 acidic aqueous solutions；Stream
Speed is 0.5-2.0ml/L；Detector is differential refraction detector or EISD；Chromatographic column is sugar, alcohol, organic acid
Analyze chromatographic column specially, 87-H, 87-Ca, 87-N series.
Embodiment 1
The extraction of polyalcohol in sorbierite hydrocracking rectifying alkoxide mixt
500g sorbierite hydrocracking rectifying alkoxide mixts, alkoxide mixt each component are added in 1000ml extractors
Content is respectively：Acylate 30wt%, dihydric alcohol 55wt%, polyalcohol dehydration product 15% is (based on the total of alkoxide mixt
Quality, similarly hereinafter), wherein the gross mass of polyalcohol is 350g, seals extractor, is passed through carbon dioxide and is forced into 10MPa,
When extractor gradually being warming up into 120 DEG C, start timing, extraction stops heating after 8 hours, will gradually be dissolved with the super of polyalcohol
Critical carbon dioxide pressure release is transferred in one-level knockout drum, is detected and is calculated the polyalcohol total amount in carbon dioxide for 315g, protects
The pressure for holding one-level knockout drum is 8MPa, and 50 DEG C of keeping temperature after standing 3 hours, carbon dioxide is transferred to and adds alcohol in advance
In the second-order separation tank of the polypropylene glycerol aether of salt mixture quality 1%, detect and to calculate the polyalcohol in carbon dioxide total
Measure as 315g, holding pressure is 5MPa, temperature is gradually decreased to 40 DEG C, stands 5 hours；By in one-level knockout drum and the second-order separation tank
Polyalcohol merge, obtain target product, the polyol quality being obtained by extraction is 329.8g, and total extraction yield of polyalcohol reaches
94.23%.It is 850ppm that alkoxide mixt in extractor, which does polyalcohol residual concentration in fixed-end forces, gaseous carbon dioxide,.
Embodiment 2
The extraction of polyalcohol in glucose hydrogenation cracking rectifying alkoxide mixt
Added in 1000ml extractors organic in 500g glucose hydrogenations cracking rectifying alkoxide mixt, alkoxide mixt
Hydrochlorate 20wt%, dihydric alcohol 62wt%, wherein polyalcohol dehydration product 18wt%, the gross mass of polyalcohol are 400g, sealing extraction
Tank is taken, carbon dioxide is passed through and is forced into 12MPa, when extractor gradually being warming up into 60 DEG C, starts timing, extraction 5 is small
When after stop heating, gradually the supercritical carbon dioxide pressure release for being dissolved with polyalcohol is transferred in one-level knockout drum, detection simultaneously
It is 380g to calculate the polyalcohol total amount in carbon dioxide, and the pressure for keeping one-level knockout drum is 9MPa, and 40 DEG C of keeping temperature is stood
After 1 hour, carbon dioxide is transferred to the two of the polyoxyethylene polyoxypropylene glycerin ether for adding alkoxide mixt quality 2% in advance
In level knockout drum, detect and calculate the polyalcohol total amount in carbon dioxide for 315g, holding pressure is 7MPa, and temperature is gradually decreased to
45 DEG C, stand 6 hours；Polyalcohol in one-level knockout drum and the second-order separation tank is merged, target product is obtained, is obtained by extraction
Polyol quality is 374.4g, and total extraction yield of polyalcohol reaches 93.6%.Alkoxide mixt in extractor does fixed-end forces,
Polyalcohol residual concentration is 1000ppm in gaseous carbon dioxide.
Embodiment 3
The extraction of polyalcohol in xylitol hydrocracking rectifying alkoxide mixt
Added in 1000ml extractors organic in 500g xylitol hydrocracking rectifying alkoxide mixts, alkoxide mixt
Hydrochlorate 25wt%, dihydric alcohol 70wt%, wherein polyalcohol dehydration product 5wt%, the gross mass of polyalcohol are 375g, sealing extraction
Tank, is passed through carbon dioxide and is forced into 18MPa, when extractor gradually being warming up into 160 DEG C, starts timing, and extraction 12 is small
When after stop heating, gradually the supercritical carbon dioxide pressure release for being dissolved with polyalcohol is transferred in one-level knockout drum, detection simultaneously
It is 363.75g to calculate the polyalcohol total amount in carbon dioxide, keeps the pressure of one-level knockout drum for 12MPa, 70 DEG C of keeping temperature,
After standing 5 hours, carbon dioxide is transferred to the polyoxyethylene polyoxypropylene season penta for adding alkoxide mixt quality 0.5% in advance
In the second-order separation tank of four alcohol ethers, detect and calculate the polyalcohol total amount in carbon dioxide for 315g, holding pressure is 0MPa, temperature
Degree is gradually decreased to 80 DEG C, stands 10 hours；Polyalcohol in one-level knockout drum and the second-order separation tank is merged, target production is obtained
Thing, the polyol quality being obtained by extraction is 374.4g, and total extraction yield of polyalcohol reaches 90.59%.Alkoxide in extractor is mixed
It is 430ppm that compound, which does polyalcohol residual concentration in fixed-end forces, gaseous carbon dioxide,.
Embodiment 4
The extraction of polyalcohol in sucrose hydrocracking rectifying alkoxide mixt
Organic acid in 500g sucrose hydrocracking rectifying alkoxide mixts, alkoxide mixt is added in 1000ml extractors
Salt 40wt%, dihydric alcohol 45wt%, wherein polyalcohol dehydration product 15wt%, the gross mass of polyalcohol are 300g, sealing extraction
Tank, is passed through carbon dioxide and is forced into 25MPa, when extractor gradually being warming up into 180 DEG C, starts timing, extracts 3 hours
Stop heating afterwards, gradually the supercritical carbon dioxide pressure release for being dissolved with polyalcohol is transferred in one-level knockout drum, detects and counts
It is 315g to calculate the polyalcohol total amount in carbon dioxide, and the pressure for keeping one-level knockout drum is 15MPa, and 80 DEG C of keeping temperature stands 2
After hour, carbon dioxide is transferred to the second-order separation for the polypropylene glycerol aether for adding alkoxide mixt quality 0.8% in advance
In tank, detect and calculate the polyalcohol total amount in carbon dioxide for 315g, holding pressure is 2MPa, and temperature is gradually decreased to 60 DEG C,
Stand 8 hours；Polyalcohol in one-level knockout drum and the second-order separation tank is merged, target product is obtained, what is be obtained by extraction is polynary
Alcohol quality is 272g, and total extraction yield of polyalcohol reaches 90.67%.Alkoxide mixt in extractor does fixed-end forces, gaseous state
Polyalcohol residual concentration is 1300ppm in carbon dioxide.
Embodiment 5
The extraction of polyalcohol in mannitol hydrocracking rectifying alkoxide mixt
Added in 1000ml extractors organic in 500g mannitol hydrocracking rectifying alkoxide mixts, alkoxide mixt
Hydrochlorate 20wt%, dihydric alcohol 75wt%, wherein polyalcohol dehydration product 5wt%, the gross mass of polyalcohol are 400g, sealing extraction
Tank, is passed through carbon dioxide and is forced into 15MPa, when extractor gradually being warming up into 150 DEG C, starts timing, extracts 7 hours
Stop heating afterwards, gradually the supercritical carbon dioxide pressure release for being dissolved with polyalcohol is transferred in one-level knockout drum, detects and counts
It is 315g to calculate the polyalcohol total amount in carbon dioxide, and the pressure for keeping one-level knockout drum is 10MPa, and 75 DEG C of keeping temperature is stood
After 2.5 hours, carbon dioxide is transferred to two fractions of the polypropylene glycerol aether for adding alkoxide mixt quality 0.7% in advance
From in tank, detecting and calculating the polyalcohol total amount in carbon dioxide for 315g, holding pressure is 4MPa, and temperature is gradually decreased to 50
DEG C, stand 7 hours；Polyalcohol in one-level knockout drum and the second-order separation tank is merged, target product is obtained, what is be obtained by extraction is more
First alcohol quality is 368g, and total extraction yield of polyalcohol reaches 92%.Alkoxide mixt in extractor does fixed-end forces, gaseous state two
Polyalcohol residual concentration is 1100ppm in carbonoxide.
Comparative example 1
100g sorbierite hydrocracking rectifying alkoxide mixts, alkoxide mixt each group are added in 1000ml three-necked flasks
Point content is respectively：Acylate 30wt%, dihydric alcohol 55wt%, polyalcohol dehydration product 15% is (based on alkoxide mixt
Gross mass, similarly hereinafter), wherein the gross mass of polyalcohol is 70g, adds 400g n-butanols and is diluted to uniform solution to it.Unlatching is stirred
Mix, the concentrated sulfuric acid is added into solution and is acidified to PH=3, acidifying terminates.After the inorganic salts filtering of precipitation, filtrate passes through backflow,
So that organic acid and n-butanol carry out esterification, production butyl formate, butyl acetate and butyl lactate, the water of generation are discharged
Consersion unit.After reaction terminates, reaction solution is washed with sodium bicarbonate solution, by the n-butanol in the solution after washing and
Remaining polyalcohol in various organic acid esters distillations, reactor, polyalcohol surplus ratio reaches 87.5%.
Above example and comparative example can be seen that：
Supercritical carbon dioxide can be up to 94% to the extraction yield of the polyalcohol in alkoxide mixt, but to acylate
But it can not extract, the separation of acylate and polyalcohol in alkoxide mixt can be realized well.
Alkoxide mixt in comparative example is by the steps such as dilution, acidifying, filtering, esterification, distillation, disengaging time length, effect
Rate is low, the 1/5 of the rate of recovery in the present invention that the one-pot polyalcohol rate of recovery is not enough.
Claims (10)
1. the method that supercritical carbon dioxide extracting separates alkoxide mixt, comprises the following steps：
A) alkoxide mixt is added in extractor, by extractor it is closed after, supercritical carbon dioxide is passed through, to alkoxide mixt
In polyalcohol extracted, the supercritical carbon dioxide for being dissolved with polyalcohol is transferred to one-level knockout drum；
B) keep the pressure and temperature in one-level knockout drum to be less than extractor, but still keep the supercriticality of carbon dioxide, quilt
The polyalcohol extracted is separated from carbon dioxide, after standing separation, through separating dissolved with a small amount of polyalcohol
Supercritical carbon dioxide is admitted to the second-order separation tank；
C) defoamer is previously added in the second-order separation tank, next supercritical carbon dioxide gas will be conveyed in one-level knockout drum and is carried out
Decompression, makes carbon dioxide be changed into being changed into after gaseous state, standing separation gaseous carbon dioxide into gas recovery from supercriticality
Device.
2. according to the method described in claim 1, it is characterised in that the quality of defoamer described in step c) is alcohol in step a)
The 0.5-2wt% of salt mixture gross mass, preferably 0.7-1wt%；The defoamer is selected from alcohol ethers defoamer, preferably polyoxy second
One or more in alkene polyoxypropylene pentaerythrite ether, polypropylene glycerol aether and polyoxyethylene polyoxypropylene glycerin ether.
3. according to the method described in claim 1, it is characterised in that the pressure of supercritical carbon dioxide described in step a) extractors
Power is 10-25MPa, preferably 12-18MPa；Temperature is 60-180 DEG C, preferably 120-160 DEG C.
4. according to the method described in claim 1, it is characterised in that in step b) one-level knockout drum, the overcritical dioxy
It is 8-15MPa, preferably 9-12MPa to change carbon pressure power；Temperature is 40-80 DEG C, preferably 50-70 DEG C.
5. according to the method described in claim 1, it is characterised in that the gross mass based on alkoxide mixt, the alkoxide mixing
Thing includes following components：
Dihydric alcohol 55-75wt%, including ethylene glycol, 1,2-PD, 2,3-butanediol, 1,2- butanediols and BDO
In one or more；
One or more in acylate 20-30wt%, including formates, lactate and acetate；
Other materials 5-15wt%, including glycerine, anhydrous sorbitol, dehydration xylitol and one kind in glycidol ether or
It is a variety of.
6. method according to claim 1 or 5, it is characterised in that the source of the alkoxide mixt is that carbon number is 6
Alkoxide mixt to 12 multi-sugar alcohol hydrocracking liquid rectifying, the carbon number includes for 6 to 12 multi-sugar alcohol
One or more in glucose, fructose, maltose, sorbierite, mannitol and xylitol.
7. the method according to any one of claim 1-6, it is characterised in that described in step c) the second-order separation tank
Pressure carbon dioxide is 0-7MPa, preferably 3-5MPa；Temperature is 40-80 DEG C, preferably 45-60 DEG C.
8. the method according to any one of claim 1-7, it is characterised in that in the step a), the extraction time
For 3-12 hours, preferably 5-8 hours.
9. the method according to any one of claim 1-8, it is characterised in that the time of repose described in step b) is 1-
4 hours, preferably 2-3 hours.
10. the method according to any one of claim 1-9, it is characterised in that the time of repose described in step c) is
5-10 hours, preferably 6-8 hours.
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