CN107867995A - The concentrate equipment of the fluid of compound containing acetyl-propionic acid - Google Patents
The concentrate equipment of the fluid of compound containing acetyl-propionic acid Download PDFInfo
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- CN107867995A CN107867995A CN201610849416.XA CN201610849416A CN107867995A CN 107867995 A CN107867995 A CN 107867995A CN 201610849416 A CN201610849416 A CN 201610849416A CN 107867995 A CN107867995 A CN 107867995A
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- propionic acid
- fluid
- membrane
- compound containing
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a kind of concentrate equipment of the fluid of compound containing acetyl-propionic acid, mainly solve the problems, such as that prior art has that yield in acetyl-propionic acid compound purge process is low and high energy consumption.The present invention comprises at least pre-filtering film and milipore filter by using along fluid flow direction;Wherein, the pre-filtering film includes filter paper film or ceramic filtration membrane, the technical scheme that the ultrafiltration membrane material is selected from least one of Kynoar, polyvinyl chloride, polysulfones, polysulfonamides, makrolon and polystyrene preferably solves the problem, in the industrial production available for purification acetyl-propionic acid compound.
Description
Technical field
The present invention relates to a kind of concentrate equipment of the fluid of compound containing acetyl-propionic acid.
Background technology
Modern chemical industry produces substantial amounts of fuels and chemicals based on fossil resource, has greatly promoted society
Development and progress.In the long run, it is limited as non-renewable physical resources, fossil resource reserves.Fossil resource can not be again
Natural disposition, people are promoted actively to find and develop renewable resources, continuously production meets growing social demand.It is raw
Material have received extensive concern as a large amount of reproducible physical resources.Levulic acid (LA, LA or penta
Every ketone acid) it is important biomass platform chemicals, low toxicity, there is hygroscopicity, distill under normal pressure and hardly decompose, intramolecular contains
Abundant functional group, it is prone to be esterified, be hydrogenated with, being condensed, aoxidizing and the series of chemical such as halogenation, be prepare it is a variety of high attached
The important intermediate of value added chemical products, it is widely used in the industry neck such as spices, solvent, oil dope, medicine and plasticizer
Domain.It is short-chain fatty acid ester from ester type compound derived from levulic acid, boiling point is higher, and a kind of important organises
Product, spices, food additives, gasoline additive and biological liquid fuel etc. can be directly used as, available for food, cosmetics,
The industries such as medicine, plastics and communications and transportation.
At present, preparation of the people to levulic acid expands research.But up to the present, the separation of levulic acid is reported not
It is common.Document CN200510061760.4 is disclosed using resin adsorption method separating and purifying technology.This method passes through reaction solution
Weak-base ion-exchange resin post, sugar is eluted using deionized water afterwards and waits not adsorbing contaminant, then eluted and adsorbed with aqueous acid
Levulic acid and formic acid on resin, obtained levulic acid and the mixed solution of formic acid pass through air-distillation and vacuum distillation
Levulic acid, yield 85%, purity 98.5% can be obtained.This method energy consumption is low, and selectivity is high, but can not remove oligosaccharide
Deng impurity, while production capacity is not high, and resin needs frequently elution, it is necessary to which a large amount of eluting solvents, the service life of resin is not high.
In addition, the method for taking organic solvent to extract also has research, such as methyl iso-butyl ketone (MIBK) (US2684981), n-butanol and acetic acid fourth
Ester (RU2174509), sec-octyl alcohol (chemical industry and engineering, 2002,19 (2):163-166) and aliphatic diamine (Separation
and Purification Technology,2000 21(1-2):165-179.).But the efficiency of solvent extraction method needs to be carried
Height, and the problem of high energy consumption be present in evaporation solvent.
Generally, existing levulic acid separation method separative efficiency is not high.Major reason with the system in levulic acid
During standby, the impurity product such as humus and tannic acid is inevitably produced.These impurity are in levulic acid distillation or rectifying
Purification phase can further be reacted with levulic acid, significantly reduce levulic acid yield.In addition, what existing preparation method obtained
Levulic acid mother liquid concentration is relatively low (10~40%), therefore by way of traditional water evaporation reaches enriched product, exists
The problems such as high energy consumption, yield is low, and purifying cost is high.
The content of the invention
The technical problems to be solved by the invention are that prior art has yield in acetyl-propionic acid compound purge process
A kind of the problem of low and high energy consumption, there is provided concentrate equipment of the new fluid of compound containing acetyl-propionic acid.The equipment has separation
The characteristics of efficiency high, low energy consumption.
In order to solve the above technical problems, the technical scheme that the present invention takes is as follows:A kind of logistics of chemical combination containing acetyl-propionic acid
The concentrate equipment of body, pre-filtering film and milipore filter are comprised at least along fluid flow direction;Wherein, the pre-filtering film includes filter paper
Film or ceramic filtration membrane, the ultrafiltration membrane material are selected from Kynoar, polyvinyl chloride, polysulfones, polysulfonamides, makrolon and gathered
At least one of styrene.
In above-mentioned technical proposal, the membrane aperture of the filter paper film or ceramic filtration membrane is 0.01~150um.
In above-mentioned technical proposal, the operation temperature of the filter paper film or ceramic filtration membrane is 0~120 DEG C, operating pressure 0.1
~10MPa.
In above-mentioned technical proposal, it is inorganic that the ceramic filtration membrane includes at least one of aluminum oxide, titanium oxide or zirconium oxide
Material.
In above-mentioned technical proposal, the milipore filter operation temperature is 1~78 DEG C, and operating pressure is 0.2~15MPa.
In above-mentioned technical proposal, further, the equipment also includes reverse osmosis membrane.
In above-mentioned technical proposal, the reverse osmosis membrane material is cellulose acetate, polyamide or cellulose acetate and gathered
The composite membrane of acid amides.
In above-mentioned technical proposal, the reverse osmosis membrane operation temperature is 5~80 DEG C, and operating pressure is 2~20MPa.
In above-mentioned technical proposal, further, the equipment also includes destilling tower.
In above-mentioned technical proposal, the acetyl-propionic acid compound has structure formula (I):
In formula (I), R1For the C optionally substituted1-8Straight or branched alkyl, the C optionally substituted2-8Straight or branched alkenyl;R2
The C for hydrogen, optionally substituted1-10Straight or branched alkyl, n are 1~6 positive integer.
In above-mentioned technical proposal, in the fluid of the compound containing acetyl-propionic acid, the content of levulic acid is 1~40 weight
Measure %.
The present invention is easy to and acetyl-propionic acid by being eliminated before the distillation and concentration purge process of routine by UF membrane
The materials such as humus, tannin and the tannic acid of compound reaction, and further removed water by reverse osmosis membrane, enriched product, from
And improve the yield of levulic acid.Compared with traditional distillating method, the mistake in the concentration of acetyl-propionic acid compound is avoided
Cheng Zhong, the problem of acetyl-propionic acid compound yield is not high caused by the reaction of acetyl-propionic acid compound and impurity so that
Follow-up distillation or rectification step is easily achieved, and reduces energy consumption, improves the economy of process, have cost it is low, separation effect
Rate is high and easily industrializes the characteristics of amplification.The acetyl-propionic acid product of yield up to 99% can be obtained using the equipment.
Embodiment
Heretofore described acetyl-propionic acid compound has structure formula (I):
In formula (I), R1For the C optionally substituted1-8Straight or branched alkyl, the C optionally substituted2-8Straight or branched alkenyl,
It is preferred that the C optionally substituted1-4Straight or branched alkyl, more preferably methyl;R2The C for hydrogen, optionally substituted1-10Straight or branched alkane
Base, preferably hydrogen, the C optionally substituted1-5Straight or branched alkyl, more preferably hydrogen;N be 1~6 positive integer, preferably n be 1~
4 positive integer, more preferably n are 2.For example, the acetyl-propionic acid compound include levulic acid, methyl ester levulinate,
Ethyl levulinate, Butyl acetylpropanoate.
As one embodiment of the present invention, the fluid biomass derived material of the compound containing acetyl-propionic acid
Hydrolyzate.
As one embodiment of the present invention, the fluid of the compound containing acetyl-propionic acid is derived from xylitol, Portugal
The hydrolyzate of at least one of grape sugar, cellobiose, cellulose, hemicellulose and lignin;Or derived from paper mill sludge,
The hydrolyzate of at least one of waste paper, bagasse, glucose, timber, corncob, corn stalk and rice straw.
As an embodiment of the invention, to containing acetyl-propionic acid using the biological material as described in raw material derivative
There is no particular limitation for the method for the fluid of compound, can use those conventionally known in the art.For example, it is described to spread out
Generation method, which can such as include making the biological material to carry out catalyzed conversion, (for example hydrolysis deoxidation, inorganic acid-catalyzed hydrolysis, to be had
Machine acid-catalyzed hydrolysis, solid acid catalysis hydrolysis, molecular screen catalytic hydrolysis, supercritical hydrolysis, catalyzing part oxidation or metal chlorination
Thing is catalyzed) to manufacture the logistics of the compound containing acetyl-propionic acid (the particularly logistics containing levulic acid) the step of (such as
It may refer to Direct conversion of cellulose to levulinic acid and gamma-
Valerolactone using solid acid catalysts, Catal.Sci.Technol., 2013,3,927-931;
Production of levulinic acid and gamma-valerolactone(GVL)from cellulose using
GVL as a solvent in biphasic systems, Energy Environ.Sci., 2012,5,8199-8203;
Effective Production of Levulinic Acid from Biomass through Pretreatment
Using Phosphoric Acid, Hydrochloric Acid, or Ionic Liquid, Ind.Eng.Chem.Res.,
2014,53(29),pp 11611–11621)。
In the logistics of the compound containing acetyl-propionic acid obtained by the above method, the content of levulic acid is 1~40 weight
Measure %.In the logistics of the compound containing acetyl-propionic acid, the content of water is 40~90 weight %.It is described to contain acetyl-propionic acid
In the logistics of compound, also containing humus, tannin and tannic acid impurity is included, the content of these impurity is 0.1~20 weight %.
Just because of the presence of these impurity, if the compound containing acetyl-propionic acid using conventional distillation or rectification and purification method processing
Logistics, these impurity can further react with acetyl-propionic acid compound therein, so as to which acetyl-propionic acid be greatly reduced
The yield of compound.
The present invention provides a kind of concentrate equipment of the fluid of compound containing acetyl-propionic acid, described to carry along fluid flow direction
Dense equipment comprises at least pre-filtering film and milipore filter;Wherein, the pre-filtering film includes filter paper film or ceramic filtration membrane, the ultrafiltration
Membrane material is selected from least one of Kynoar, polyvinyl chloride, polysulfones, polysulfonamides, makrolon and polystyrene
As one embodiment of the present invention, the membrane aperture of the filter paper film or ceramic filtration membrane is 0.01~150um, mistake
It is 0~120 DEG C to filter temperature, and operating pressure is 0.1~10MPa.The ceramic filtration membrane is included in aluminum oxide, titanium oxide or zirconium oxide
At least one inorganic material.The filtered paper membrane of fluid or ceramic filtration membrane of the compound containing acetyl-propionic acid, removing solid matter,
Humus and other large granular impurities.
As one embodiment of the present invention, the ultrafiltration membrane material be selected from Kynoar, polyvinyl chloride, polysulfones,
At least one of polysulfonamides, makrolon and polystyrene.The milipore filter operation temperature is 1~78 DEG C, operating pressure
For 0.2~15MPa.Milipore filter can molecular cut off be more than 1000 compound, for example, humus, tannin and tannin
Acid.
As one embodiment of the present invention, further, the equipment also includes reverse osmosis membrane.The reverse osmosis membrane
Material is the composite membrane of cellulose acetate, polyamide or cellulose acetate and polyamide.The reverse osmosis membrane operation temperature is
5~80 DEG C, operating pressure is 2~20MPa.Reverse osmosis membrane is removing the moisture in logistics.
As one embodiment of the present invention, the equipment also includes the destilling tower after UF membrane, further to carry
It is dense.There is no particular limitation for the method for the distillation, can use those conventionally known in the art.For example, normal pressure steams
Evaporate and be evaporated under reduced pressure.
As one embodiment of the present invention, using equipment concentrate compound containing acetyl-propionic acid fluid when,
Comprise the following steps:A) logistics of the compound containing acetyl-propionic acid is made to obtain filtrate I by filter paper film or ceramic filtration membrane;
The content of acetyl-propionic acid compound is 1.1~55 weight % in filtrate I;B) filtrate I is made to obtain filtrate II by milipore filter;
The content of acetyl-propionic acid compound is 1.1~60 weight % in filtrate II;C) filtrate II is made to obtain filtrate by reverse osmosis membrane
III;The content of acetyl-propionic acid compound is 70~98 weight % in filtrate II I;D) filtrate II I distills, and obtains concentrate and refines
Acetyl-propionic acid compound afterwards, the wherein content of acetyl-propionic acid compound are 98~99.9 weight %.
Below by embodiment, the present invention is further elaborated.
【Embodiment 1】
1.5 kilograms of corn stalks are weighed, is placed in autoclave pressure and adds 10 kilograms of water, add the 5mol/L of water quality 7%
Sulfuric acid solution, be warming up at 180 DEG C and react 45 minutes, cool down afterwards, obtain the reaction solution containing levulic acid.Experiment is surveyed
Fixed, the content of levulic acid is 31%.
6kg reaction solutions are taken to exist by the aluminium oxide ceramics filter membrane that membrane aperture is 1um, control pressure 1MPa, temperature control
20 DEG C, collect permeate.
By the permeate by that can throw milipore filter of the retention more than 1000, membrane material is Kynoar, and operating pressure is
7MPa, operation temperature are 30 DEG C, collect ultrafiltration permeate.
Ultrafiltrate is passed through into the composite membrane by cellulose acetate and polyamide, reverse osmosis concentration filtering, operating pressure is
10MPa, operation temperature are 25 DEG C, are collected into 2.4kg concentrates.Obtained concentrate is evaporated under reduced pressure afterwards, temperature 110
Levulic acid cut is collected at DEG C.1.77kg levulic acids are collected into altogether, and chromatogram detection purity is 99.5%, yield 95%.
【Embodiment 2】
1.1 kilograms of corn stalks are weighed, is placed in autoclave pressure and adds 8.6 kilograms of water, add the 5mol/L of water quality 5%
Sulfuric acid solution, be warming up at 200 DEG C and react 45 minutes, cool down afterwards, obtain the reaction solution containing levulic acid.Experiment is surveyed
Fixed, the content of levulic acid is 34%.
It is the titanium oxide ceramics filter membrane that 34% reaction solution is 100um by membrane aperture to take 5kg levulic acid concentration, control pressure
Power is 4MPa, and temperature control collects permeate at 100 DEG C.
By the permeate by that can throw milipore filter of the retention more than 1000, membrane material is polyvinyl chloride, and operating pressure is
0.5MPa, operation temperature are 25 DEG C, collect ultrafiltration permeate.
Ultrafiltrate is filtered through PA membrane, reverse osmosis concentration is passed through, operating pressure 15MPa, operation temperature 80
DEG C, 1.83kg concentrates are collected into, are afterwards evaporated under reduced pressure obtained concentrate, are collected into 1.63kg levulic acids altogether,
Chromatogram detection purity is 99.2%, yield 96%.
【Embodiment 3】
The zirconia ceramics filter membrane that the reaction solution that the concentration for taking 6kg levulic acids is 28% is 60um by membrane aperture, control
Pressing pressure is 8MPa, and temperature control collects permeate at 25 DEG C.
By the permeate by that can throw milipore filter of the retention more than 1000, membrane material is makrolon, and operating pressure is
5MPa, operation temperature are 25 DEG C, collect ultrafiltration permeate.
Ultrafiltrate is passed through into the composite membrane by cellulose acetate and polyamide, reverse osmosis concentration filtering, operating pressure is
4MPa, operation temperature are 15 DEG C, are collected into 1.89kg concentrates, are afterwards evaporated under reduced pressure obtained concentrate, are collected altogether
To 1.55kg levulic acids, chromatogram detection purity is 99.4%, yield 92%.
【Embodiment 4】
The concentration for taking 5kg levulic acids is the aluminium oxide ceramics filter membrane that 35% reaction solution is 0.5um by membrane aperture, control
Pressure is 2MPa, and temperature control collects permeate at 60 DEG C.
By the permeate by that can throw milipore filter of the retention more than 1000, membrane material is makrolon, and operating pressure is
4MPa, operation temperature are 30 DEG C, collect ultrafiltration permeate.
Ultrafiltrate is passed through into the composite membrane by cellulose acetate and polyamide, reverse osmosis concentration filtering, operating pressure is
9MPa, operation temperature are 10 DEG C, are collected into 1.84kg concentrates, are afterwards evaporated under reduced pressure obtained concentrate, are collected altogether
To 1.72kg levulic acids, chromatogram detection purity is 99.9%, yield 98%.
【Embodiment 5】
The concentration for taking 4kg levulic acids is the aluminium oxide ceramics filter membrane that 37% reaction solution is 20um by membrane aperture, control
Pressure is 0.5MPa, and temperature control collects permeate at 100 DEG C.
By the permeate by that can throw milipore filter of the retention more than 1000, membrane material is Kynoar, and operating pressure is
8MPa, operation temperature are 25 DEG C, collect ultrafiltration permeate.
Ultrafiltrate is passed through into the composite membrane by cellulose acetate and polyamide, reverse osmosis concentration filtering, operating pressure is
10MPa, operation temperature are 25 DEG C, are collected into 1.72kg concentrates, are afterwards evaporated under reduced pressure obtained concentrate, are collected altogether
To 1.38kg levulic acids, chromatogram detection purity is 99.4%, yield 93%.
【Embodiment 6】
The concentration for taking 8kg levulic acids is the zirconia ceramics filter membrane that 38% reaction solution is 0.5um by membrane aperture, control
Pressure is 4MPa, and temperature control collects permeate at 30 DEG C.
The milipore filter that the permeate is more than into 1000 by that can throw retention, membrane material are polysulfones, operating pressure 6MPa, are grasped
Make temperature as 25 DEG C, collect ultrafiltration permeate.
Ultrafiltrate is filtered through cellulose acetate film, reverse osmosis concentration is passed through, operating pressure 8MPa, operation temperature is
30 DEG C, 3.45kg concentrates are collected into, are afterwards evaporated under reduced pressure obtained concentrate, are collected into 2.89kg levulinics altogether
Acid, chromatogram detection purity is 99.9%, yield 99%.
【Embodiment 7】
The concentration for taking 7kg levulic acids is the aluminium oxide ceramics filter membrane that 36% reaction solution is 0.01um by membrane aperture, control
Pressing pressure is 3MPa, and temperature control collects permeate at 10 DEG C.
By the permeate by that can throw milipore filter of the retention more than 1000, membrane material is makrolon, and operating pressure is
1MPa, operation temperature are 35 DEG C, collect ultrafiltration permeate.
Ultrafiltrate is passed through into the composite membrane by cellulose acetate and polyamide, reverse osmosis concentration filtering, operating pressure is
12MPa, operation temperature are 35 DEG C, are collected into 2.83kg concentrates, are afterwards evaporated under reduced pressure obtained concentrate, are collected altogether
To 2.42kg levulic acids, chromatogram detection purity is 99.3%, yield 96%.
【Embodiment 8】
The concentration for taking 6kg levulic acids is the zirconia ceramics filter membrane that 34% reaction solution is 40um by membrane aperture, control
Pressure is 5.5MPa, and temperature control collects permeate at 50 DEG C.
The milipore filter that the permeate is more than into 1000 by that can throw retention, membrane material are polysulfones, operating pressure 3MPa, are grasped
Make temperature as 25 DEG C, collect ultrafiltration permeate.
Ultrafiltrate is filtered through cellulose acetate film, reverse osmosis concentration is passed through, operating pressure 10MPa, operation temperature
For 60 DEG C, 2.22kg concentrates are collected into, are afterwards evaporated under reduced pressure obtained concentrate, are collected into 1.94kg levulinics altogether
Acid, chromatogram detection purity is 99.3%, yield 95%.
Claims (11)
1. a kind of concentrate equipment of the fluid of compound containing acetyl-propionic acid, comprise at least pre-filtering film along fluid flow direction and surpass
Filter membrane;Wherein, the pre-filtering film includes filter paper film or ceramic filtration membrane, and the ultrafiltration membrane material is selected from Kynoar, polychlorostyrene
At least one of ethene, polysulfones, polysulfonamides, makrolon and polystyrene.
2. the concentrate equipment of the fluid of compound containing acetyl-propionic acid according to claim 1, it is characterised in that the filter paper film
Or the membrane aperture of ceramic filtration membrane is 0.01~150um.
3. the concentrate equipment of the fluid of compound containing acetyl-propionic acid according to claim 1, it is characterised in that the filter paper film
Or the operation temperature of ceramic filtration membrane is 0~120 DEG C, operating pressure is 0.1~10MPa.
4. the concentrate equipment of the fluid of compound containing acetyl-propionic acid according to claim 1, it is characterised in that the ceramic filtering
Film includes at least one of aluminium oxide ceramics filter membrane, titanium oxide ceramics filter membrane or zirconia ceramics filter membrane.
5. the concentrate equipment of the fluid of compound containing acetyl-propionic acid according to claim 1, it is characterised in that the milipore filter
Operation temperature is 1~78 DEG C, and operating pressure is 0.2~15MPa.
6. the concentrate equipment of the fluid of compound containing acetyl-propionic acid according to claim 1, it is characterised in that further,
The equipment also includes reverse osmosis membrane.
7. the concentrate equipment of the fluid of compound containing acetyl-propionic acid according to claim 6, it is characterised in that the counter-infiltration
Membrane material is the composite membrane of cellulose acetate, polyamide or cellulose acetate and polyamide.
8. the concentrate equipment of the fluid of compound containing acetyl-propionic acid according to claim 7, it is characterised in that the counter-infiltration
Membrane operations temperature is 5~80 DEG C, and operating pressure is 2~20MPa.
9. the concentrate equipment of the fluid of compound containing acetyl-propionic acid according to claim 1, it is characterised in that further,
The equipment also includes destilling tower.
10. the concentrate equipment of the fluid of compound containing acetyl-propionic acid according to claim 1, it is characterised in that the acetyl
Group propionic acid compounds have structure formula (I):
In formula (I), R1For the C optionally substituted1-8Straight or branched alkyl, the C optionally substituted2-8Straight or branched alkenyl;R2For
Hydrogen, the C optionally substituted1-10Straight or branched alkyl, n are 1~6 positive integer.
11. the concentrate equipment of the fluid of compound containing acetyl-propionic acid according to claim 1, it is characterised in that described to contain second
In the fluid of acyl group propionic acid compounds, the content of levulic acid is 1~40 weight %.
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CN105533337A (en) * | 2015-12-16 | 2016-05-04 | 全国供销合作总社济南果蔬华德公司 | Processing method of high-quality blueberry concentrated juice with high anthocyan content |
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WO2003082450A1 (en) * | 2002-03-28 | 2003-10-09 | Nalco Company | Method of monitoring membrane separation processes |
CN1837201A (en) * | 2006-02-21 | 2006-09-27 | 张守政 | Process for extracting tea polyphenol, theanine, tea polysaccharide and tea pigment from tea |
WO2014037560A1 (en) * | 2012-09-10 | 2014-03-13 | Dsm Ip Assets B.V. | Process for the separation of levulinic acid from biomass |
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