CN111320539B - Method for storing acetoin - Google Patents
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- CN111320539B CN111320539B CN201811521995.0A CN201811521995A CN111320539B CN 111320539 B CN111320539 B CN 111320539B CN 201811521995 A CN201811521995 A CN 201811521995A CN 111320539 B CN111320539 B CN 111320539B
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- acetoin
- monomer
- molecular sieve
- acetic acid
- ion exchange
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- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title claims abstract description 47
- GFAZHVHNLUBROE-UHFFFAOYSA-N hydroxymethyl propionaldehyde Natural products CCC(=O)CO GFAZHVHNLUBROE-UHFFFAOYSA-N 0.000 title claims abstract description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 81
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002808 molecular sieve Substances 0.000 claims abstract description 49
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 25
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005342 ion exchange Methods 0.000 claims abstract description 24
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
- 238000007789 sealing Methods 0.000 claims abstract description 9
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 8
- 239000011575 calcium Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 3
- 239000003814 drug Substances 0.000 description 6
- 229940079593 drug Drugs 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 235000013599 spices Nutrition 0.000 description 5
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- CLBXCDSXUXNOIM-UHFFFAOYSA-N 3-oxidanylbutan-2-one Chemical compound CC(O)C(C)=O.CC(O)C(C)=O CLBXCDSXUXNOIM-UHFFFAOYSA-N 0.000 description 1
- YXLHUUKZPCMSFX-UHFFFAOYSA-N 4-chloro-4,5-dimethyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1(C)Cl YXLHUUKZPCMSFX-UHFFFAOYSA-N 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 244000141359 Malus pumila Species 0.000 description 1
- 239000005480 Olmesartan Substances 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- PWNMXPDKBYZCOO-UHFFFAOYSA-N Prulifloxacin Chemical compound C1=C2N3C(C)SC3=C(C(O)=O)C(=O)C2=CC(F)=C1N(CC1)CCN1CC=1OC(=O)OC=1C PWNMXPDKBYZCOO-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 241000219094 Vitaceae Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229960000723 ampicillin Drugs 0.000 description 1
- AVKUERGKIZMTKX-NJBDSQKTSA-N ampicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=CC=C1 AVKUERGKIZMTKX-NJBDSQKTSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 230000036983 biotransformation Effects 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 229940124307 fluoroquinolone Drugs 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229960005117 olmesartan Drugs 0.000 description 1
- VTRAEEWXHOVJFV-UHFFFAOYSA-N olmesartan Chemical compound CCCC1=NC(C(C)(C)O)=C(C(O)=O)N1CC1=CC=C(C=2C(=CC=CC=2)C=2NN=NN=2)C=C1 VTRAEEWXHOVJFV-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229960001224 prulifloxacin Drugs 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 235000013618 yogurt Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/86—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for storing acetoin, which comprises the following steps of (1) obtaining acetoin containing acetic acid; (2) Obtaining an acetoin monomer B from an acetoin monomer containing acetic acid through an adsorption exchange bed layer filled with a calcium ion exchange molecular sieve, and (3) sealing and storing the acetoin monomer B. The method can effectively reduce acetoin decomposition and prolong the storage time of the acetoin.
Description
Technical Field
The invention relates to a method for storing acetoin, in particular to a storage method capable of effectively reducing acetoin decomposition.
Background
Acetoin, also known as 3-hydroxybutanone, naturally exists in a plurality of foods such as corn, grapes, apples and meat, is an edible spice with wide application, has pleasant cream fragrance, is a common spice variety internationally, and is mainly used for producing spices such as cream, dairy products, yoghourt and strawberry types. The national standard GB2760-86 stipulates that the food spice is a food spice which is allowed to be used. Acetoin is also a key intermediate for synthesizing 4-chloro-4, 5-dimethyl-1, 3-dioxolane-2-one (CDMDO), can be used for modifying a plurality of medicines, greatly improves the medicine effect, and reduces the side effect of the medicines, such as the intermediate for synthesizing cardiovascular medicines, olmesartan, penicillin medicines, ampicillin and fluoroquinolone antibacterial medicines, prulifloxacin and the like.
Acetoin can be prepared by biotransformation (Jun, modern chemical industry, 2008, 28 (4): 18-22), condensation of acetoin (CN 1562934), partial hydrogenation of 2, 3-butanedione (Zhang Xiaozhou, jiangsu chemical industry, 2001,29 (2): 29-31), and halogenated hydrolysis of methyl ethyl ketone (CN 101357882).
According to the current QB/T4234-2011 < 3-hydroxy-2-butanone (acetoin) > standard in China, indexes such as purity, density, refractive index, aroma and the like of the acetoin are limited, and the acetoin purity is required to be not lower than 96%. The acetoin belongs to alpha-hydroxy ketone compounds and contains two active functional groups of a hydroxyl group and a carbonyl group. No matter which method is adopted for preparation, acetoin molecules are active in chemical property and are easy to decompose (reverse reaction of acetoin condensation) at normal temperature to generate acetaldehyde and further generate acetic acid, and when the acetic acid exceeds a certain concentration, rapid decomposition of acetoin monomers is accelerated, so that the acetoin purity is rapidly reduced. In addition, after the acid value reaches a certain value, the acetoin monomer is easy to generate oxidation reaction to generate 2, 3-butanedione, so that the quality guarantee period of the acetoin monomer is short.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for storing acetoin. The method can effectively reduce acetoin decomposition and prolong the storage time of the acetoin.
A method for storing acetoin comprises the steps of (1) obtaining acetoin containing acetic acid; (2) Obtaining an acetoin monomer B from an acetoin monomer containing acetic acid through an adsorption exchange bed layer filled with a calcium ion exchange molecular sieve, and (3) sealing and storing the acetoin monomer B.
A method for storing acetoin specifically comprises the following steps:
(1) Obtaining an acetoin monomer A with acetic acid content of 0.1-0.3wt% and purity not less than 99%;
(2) Enabling the acetoin monomer A to pass through an adsorption exchange bed layer filled with a calcium ion exchange molecular sieve to obtain an acetoin monomer B with the calcium ion content of 100-200 mu g/g;
(3) And sealing the B and storing at room temperature.
In the method, 0.1-0.3% of acetic acid contained in the acetoin monomer A in the step (1) can be prepared by artificially adding acetic acid, and can also be produced by self-decomposition of the acetoin monomer.
In the method, preferably, the acetoin monomer A with the acetic acid mass content of 0.1-0.3% and the purity of not less than 99% is generated by acetoin self-decomposition.
In the method, the acetoin monomer sample with the purity of not less than 99.5% is preferably placed for 5-10 days under the open and illumination conditions, and then the acetoin monomer A with the acetic acid mass content of 0.1-0.3% and the purity of not less than 99% can be obtained.
In the process of the present invention, the operating temperature in step (2) is from 20 to 100 ℃ and preferably from 50 to 85 ℃.
In the process of the present invention, the operating pressure in step (2) is from 0.1 to 10 MPa, preferably from 0.1 to 0.5 MPa.
In the method, the liquid hourly space velocity of the step (2) is 0.01-10 h -1 Preferably 0.01 to 0.1 h -1 。
In the method, the calcium ion exchange molecular sieve in the step (2) does not contain other metal ions for balancing the negative charge of the framework of the molecular sieve.
In the method of the present invention, preferably, the calcium ion exchange molecular sieve in step (2) is a calcium ion exchange molecular sieve which adopts a hydrogen type molecular sieve as a matrix and obtains 100% exchange calcium type molecular sieve or a partially exchanged calcium hydrogen type molecular sieve with an exchange degree not lower than 90% through calcium ion exchange. The molecular sieve can be various types of molecular sieves which are commercially available or prepared according to the existing method, and is preferably selected from at least one of MFI type, TON type and FER type molecular sieves. More preferably FER type molecular sieves, particularly at least one selected from the group consisting of ZSM-35, ferrierite, ZSM-23 and ZSM-38 molecular sieves. As a further preference, siO of the FER molecular sieve 2 /Al 2 O 3 The molar ratio is 8 to 50, preferably 15 to 20.
As a further optimization of the method, the method for preparing the specific calcium ion exchange FER molecular sieve is provided, but the method is not limited to the method, and specifically comprises the following steps:
(1) Performing ammonium ion exchange on the FER type molecular sieve for multiple times until the total mass fraction of metal ions used as negative charges of a framework of the molecular sieve is not higher than 0.001%, and filtering, drying and roasting to obtain the hydrogen FER type molecular sieve;
(2) Performing calcium ion exchange on the obtained hydrogen-type FER molecular sieve for multiple times until the calcium ion exchange degree is more than 90%, preferably more than 95%, more preferably 100%, filtering, drying, and roasting to obtain calcium ion exchange molecular sieve Ca/FER
As a further preferred method of the present invention, a specific method for storing acetoin is provided, but the method of the present invention is not limited, and specifically includes the following steps:
(1) Placing an acetoin monomer with the purity of more than 99.5% in an open place under the illumination condition for 5-10 days to obtain an acetoin monomer A when the mass content of acetic acid reaches 0.1-0.3%;
(2) Making A pass through an adsorption exchange bed filled with Ca/FER molecular sieve under the conditions of 0.1-0.5 MPa, 50-85 ℃ and liquid airspeed of 0.01-0.1 to obtain an acetoin monomer B with calcium metal ion content of 100-200 mu g/g;
(3) And sealing the B and storing at room temperature.
One of the effects and benefits of the invention is that the preservation time of the acetoin monomer is effectively prolonged.
Detailed Description
The action and effect of the process of the present invention will be further illustrated by the following examples and comparative examples, but the following examples are not intended to limit the present invention.
In the following examples, the acetoin monomer Z used was prepared by dehydrogenation of 2, 3-butanediol. The purity of the acetoin monomer Z is more than 99.7 percent and the acid value is less than 0.01 mg KOH The mass content of the acetic acid is less than 0.001 percent by weight after conversion. The content of Na ions and Ca ions of the acetoin monomer Z is lower than 0.1 mu g/g by adopting an ICP method.
In the following examples, the molecular sieve for calcium ion exchange is a Ca/FER molecular sieve, and the specific preparation method is as follows: 200 g of SiO 2 /Al 2 O 3 NaK-FER molecular sieve with a molar ratio of 17.1, 214 g of NH 4 Mixing Cl and 4000 g of deionized water, pulping, stirring at 75 ℃ for 5 hours, filtering, repeating the exchange process at 75 ℃ for 5 times, and performing exchangeFiltering, washing the obtained filter cake with deionized water, drying at 110 deg.C and calcining at 550 deg.C to obtain hydrogen-type FER molecular sieve (HFER), wherein Na is 2 O and K 2 The total content of O is less than 0.001 percent. A sample of HFER was taken at 100 g,222 g CaCl 2 Mixing with 2000 g of deionized water, pulping, stirring for 5 hours at 75 ℃, filtering, repeating the exchange process for 5 times at 75 ℃, filtering after exchange, drying for 12 hours at 110 ℃, roasting for 8 hours at 550 ℃, and marking the obtained sample as Ca/FER.
The Ca and Al contents of Ca/FER were determined by ICP-AES method. Assume Ca 2+ Balancing the negative charge of the alundum tetrahedron, so that at a Ca/Al molar ratio of 0.5, ca is present 2+ The degree of exchange was 100%. Ca 2+ The exchange degree calculation method comprises the following steps:
wherein A is Ca And A Al Respectively, the molar mass concentrations of Ca and Al in the sample, mol/g.
The exchange degree of Ca/FER molecular sieves used in the following examples was determined to be more than 95% by the ICP-AES method
Comparative example 1
A commercially available analytically pure acetoin monomer (C-0-1) was used as a sample, and Na was added in an amount of 184.4. Mu.g/g to the C-0-1 sample by ICP measurement + As a stabilizer.
The change of each index with the standing time was observed, and the results are shown in Table 1. The purity initial measurement value of a commercially available acetoin monomer sample is 99.7%, and the standard requirement of QB/T4234-2011 is met. When a commercial acetoin monomer sample is unsealed, although the sample is still stored under sealed and backlight conditions after sampling analysis, when the sample is unsealed again for analysis and detection, the acid value is obviously increased gradually, and the acetoin purity is gradually reduced. Particularly, when the acid value exceeds a certain value (4 mgKOH/g), the purity reduction rate of acetoin is obviously accelerated. After 60 days after the opening of the additive sample, the acetoin purity index of the additive sample is reduced to 95.8 percent and is lower than the minimum requirement (96 percent) of QB/T4234-2011 standard.
Watch (CN)
Example 1
(1) Placing an acetoin monomer Z prepared by a dehydrogenation method under the condition of illumination for 10 days after opening, and measuring the mass content of acetic acid to be 0.28% to obtain an acetoin monomer A-1; (2) The A-1 is maintained at 0.1MPa, 85 ℃ and the liquid space velocity of 0.1 h -1 Obtaining acetoin monomer B-1 through an adsorption exchange bed filled with Ca/FER molecular sieve under the condition, and measuring Ca of B-1 by adopting ICP 2+ The content is 117 mug/g; (3) The C-1 sample was obtained by sealing B-1 in a narrow-mouth bottle and stored at room temperature. The change of each index of the C-1 sample with the standing time was measured, and the results are shown in Table 2.
TABLE 2
Example 2
(1) Adding a proper amount of analytically pure acetic acid into an acetoin monomer Z prepared by a dehydrogenation method to prepare an acetoin monomer A-2 containing 0.12 mass percent of acetic acid; (2) The A-2 is led to be at 0.5MPa, 50 ℃ and the liquid space velocity of 0.01 h -1 Obtaining acetoin monomer B-2 through an adsorption exchange bed filled with Ca/FER molecular sieve under the condition, and measuring Ca of B-2 by adopting ICP 2+ The content is 163 mug/g; (3) The C-2 sample was obtained by sealing B-2 in a narrow-necked flask and stored at room temperature. The C-2 sample was measured for various indices as a function of the standing time, and the results are shown in Table 3.
TABLE 3
Example 3
(1) Placing an acetoin monomer Z prepared by a dehydrogenation method under the condition of illumination for 5 days after opening, and measuring the mass content of acetic acid to be 0.21% to obtain an acetoin monomer A-3; (2) The A-3 is led to be at 0.1MPa, 75 ℃ and the liquid space velocity of 0.05 h -1 Obtaining acetoin monomer B-3 through an adsorption exchange bed filled with Ca/FER molecular sieve under the condition, and measuring Ca of B-3 by adopting ICP 2+ The content is 193 mug/g; (3) The C-3 sample was obtained by sealing B-3 in a narrow-necked flask and stored at room temperature. The C-3 sample was tested for various indicators as a function of time of standing and the results are shown in Table 4.
TABLE 4
Claims (9)
1. A method for storing acetoin is characterized by comprising the following steps: comprises (1) obtaining acetoin A containing acetic acid; (2) Obtaining an acetoin monomer B from an acetoin monomer A containing acetic acid through an adsorption exchange bed layer filled with a calcium ion exchange molecular sieve, and (3) hermetically storing the acetoin monomer B;
in the acetoin A containing acetic acid in the step (1), the mass content of the acetic acid is 0.1-0.3wt%, and the purity is not lower than 99%;
the calcium ion exchange molecular sieve in the step (2) adopts a hydrogen type molecular sieve as a matrix, and a calcium type molecular sieve with 100 percent of exchange or a partially exchanged calcium hydrogen type molecular sieve with the exchange degree not lower than 90 percent is obtained through calcium ion exchange; the calcium ion exchange molecular sieve is FER type molecular sieve, and is selected from at least one of ZSM-35, ferririte, ZSM-23 and ZSM-38 molecular sieves, and SiO of the FER molecular sieve 2 /Al 2 O 3 The molar ratio is 8-50;
the operation conditions of the acetoin monomer A in the step (2) passing through the adsorption exchange bed layer filled with the calcium ion exchange molecular sieve are as follows: the operation temperature is 20-100 ℃; the operating pressure is 0.1-10 MPa; the liquid hourly space velocity is 0.01-10 h -1 。
2. The method of claim 1, wherein: the method specifically comprises the following steps:
(1) Obtaining acetoin monomer A with acetic acid mass content of 0.1wt% -0.3wt% and purity not lower than 99%;
(2) Enabling the acetoin monomer A to pass through an adsorption exchange bed layer filled with a calcium ion exchange molecular sieve to obtain an acetoin monomer B with the calcium ion content of 100-200 mu g/g;
(3) And sealing the B and storing at room temperature.
3. The method of claim 2, wherein: the acetoin monomer A in the step (1) contains acetic acid with the mass content of 0.1% -0.3%, and is obtained by artificially adding acetic acid or by adopting acetoin monomer self-decomposition.
4. The method of claim 3, wherein: the acetoin monomer A with the acetic acid mass content of 0.1% -0.3% and the purity of not less than 99% is obtained by acetoin self-decomposition.
5. The method of claim 4, wherein: and (3) placing the acetoin monomer sample with the purity of not less than 99.5% for 5-10 days under the conditions of opening and illumination to obtain the acetoin monomer A with the acetic acid mass content of 0.1% -0.3% and the purity of not less than 99%.
6. The method of claim 2, wherein: the operation temperature of the step (2) is 20-100 ℃; the operating pressure is 0.1-10 MPa; the liquid hourly space velocity is 0.01-10 h -1 。
7. The method of claim 6, wherein: the operation temperature of the step (2) is 50-85 ℃; the operating pressure is 0.1-0.5 MPa; the liquid hourly space velocity is 0.01-0.1 h -1 。
8. The method of claim 2, wherein: the preparation method of the calcium ion exchange molecular sieve comprises the following steps:
(1) Performing ammonium ion exchange on the FER type molecular sieve for multiple times until the total mass fraction of metal ions used as negative charges of a framework of the balanced molecular sieve is not higher than 0.001%, and filtering, drying and roasting to obtain the hydrogen FER type molecular sieve;
(2) And (2) performing calcium ion exchange on the hydrogen-type FER molecular sieve obtained in the step (1) for multiple times until the calcium ion exchange degree is over 90%, and filtering, drying and roasting to obtain the Ca/FER of the calcium ion exchange molecular sieve.
9. The method of claim 1, wherein: the method specifically comprises the following steps:
(1) Placing an acetoin monomer with the purity of more than 99.5wt% under the illumination condition for 5-10 days after the open, and obtaining an acetoin monomer A when the mass content of acetic acid reaches 0.1-0.3 wt%;
(2) Making A pass through an adsorption exchange bed filled with Ca/FER molecular sieve under the conditions of 0.1-0.5 MPa, 50-85 ℃ and liquid airspeed of 0.01-0.1 to obtain an acetoin monomer B with calcium metal ion content of 100-200 mu g/g;
(3) And sealing the B and storing at room temperature.
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|---|---|---|---|
| CN201811521995.0A CN111320539B (en) | 2018-12-13 | 2018-12-13 | Method for storing acetoin |
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|---|---|---|---|
| CN201811521995.0A CN111320539B (en) | 2018-12-13 | 2018-12-13 | Method for storing acetoin |
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| CN111320539B true CN111320539B (en) | 2023-02-03 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924253A (en) * | 2012-11-20 | 2013-02-13 | 南京工业大学 | Method for extracting acetoin from fermentation liquor |
| CN106588617A (en) * | 2016-11-15 | 2017-04-26 | 大连理工大学 | Method for separating and purifying acetoin in fermentation liquor |
| CN108017498A (en) * | 2016-10-31 | 2018-05-11 | 中国石油化工股份有限公司 | Remove the method and the production method of cyclohexyl acetate and the production method of cyclohexanol of acetic acid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924253A (en) * | 2012-11-20 | 2013-02-13 | 南京工业大学 | Method for extracting acetoin from fermentation liquor |
| CN108017498A (en) * | 2016-10-31 | 2018-05-11 | 中国石油化工股份有限公司 | Remove the method and the production method of cyclohexyl acetate and the production method of cyclohexanol of acetic acid |
| CN106588617A (en) * | 2016-11-15 | 2017-04-26 | 大连理工大学 | Method for separating and purifying acetoin in fermentation liquor |
Non-Patent Citations (2)
| Title |
|---|
| Recovery of Acetoin from the Ethanol−Acetoin−Acetic Acid Ternary Mixture Based on Adsorption Methodology Using a Hyper-Cross-Linked Resin;Jinglan Wu等;《Industrial & Engineering Chemistry Research》;20140714;第53卷;12411-12419 * |
| 生物法制备平台化合物乙偶姻的最新研究进展;刘晓霏等;《中国生物工程杂志》;20151231;第35卷(第10期);91-99 * |
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