CN117164451A - Enrichment method of caproic acid in brewing byproducts and application thereof - Google Patents
Enrichment method of caproic acid in brewing byproducts and application thereof Download PDFInfo
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- CN117164451A CN117164451A CN202311138331.7A CN202311138331A CN117164451A CN 117164451 A CN117164451 A CN 117164451A CN 202311138331 A CN202311138331 A CN 202311138331A CN 117164451 A CN117164451 A CN 117164451A
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000006227 byproduct Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 101
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 239000003480 eluent Substances 0.000 claims abstract description 33
- 238000001179 sorption measurement Methods 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 25
- 238000010828 elution Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 23
- 238000011068 loading method Methods 0.000 claims description 22
- 239000008234 soft water Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 6
- 240000008042 Zea mays Species 0.000 claims description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 6
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 235000005822 corn Nutrition 0.000 claims description 6
- 235000013305 food Nutrition 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 abstract description 20
- 235000014101 wine Nutrition 0.000 abstract description 14
- 238000005886 esterification reaction Methods 0.000 abstract description 9
- 230000032050 esterification Effects 0.000 abstract description 6
- 150000002148 esters Chemical class 0.000 abstract description 4
- 239000013589 supplement Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000005086 pumping Methods 0.000 description 5
- 238000000855 fermentation Methods 0.000 description 4
- 230000004151 fermentation Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013124 brewing process Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 235000020097 white wine Nutrition 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides an enrichment method of caproic acid in a brewing byproduct and application thereof, wherein the enrichment method comprises the following steps: adsorbing, washing and eluting caproic acid in the brewing byproducts by adopting a chromatographic column to obtain high-concentration eluent; the chromatographic column comprises macroporous adsorption resin; the eluent adopted by the elution comprises ethanol solution; the high-concentration eluent is ethanol solution of caproic acid. According to the enrichment method, the caproic acid in the brewing byproducts can be enriched efficiently, so that a high-concentration caproic acid-ethanol system is achieved by a low-concentration caproic acid-water system, the concentration of the caproic acid is improved obviously, and the esterification of the caproic acid is facilitated, so that the high-ester flavoring wine of high-concentration ethyl caproate is obtained; not only solves the problem of emission of brewing byproducts, but also can be recycled, supplements esters in the middle and rear stage wine, and improves the quality of white spirit.
Description
Technical Field
The invention belongs to the technical field of white spirit production, and particularly relates to a method for enriching caproic acid in a brewing byproduct and application thereof.
Background
In the brewing process of solid strong aromatic Chinese spirits, distilled liquor is divided into head liquor, middle liquor and tail liquor. Acid is washed after the wine is taken out, namely, a part of organic acids such as caproic acid, butyric acid and acetic acid in the fermented grains are volatilized, the acidity of the fermented grains is reduced so as to facilitate the next round of fermentation, the steam with the organic acids volatilized in the acid washing process is changed into acid water after being condensed, the acid water belongs to brewing byproducts, and the direct discharge can cause environmental pollution.
The current strong aromatic white spirit accounts for about 70% of the sales volume of the white spirit in China and is deeply favored by consumers. Ethyl caproate is a main flavor component of the Luzhou-flavor liquor, and the content of ethyl caproate is one of important factors for determining the quality of the Luzhou-flavor liquor. Under the condition of natural fermentation, the process of converting caproic acid into ethyl caproate through esterification is slower, so that the content of ethyl caproate in the final fermented grains is lower than the yield of the base wine, and the defect of ethyl caproate is generally overcome by a method of prolonging the fermentation period in production, but the production cycle is reduced, and the production efficiency is reduced. In addition, during distillation, ethyl caproate is mainly distilled out in the front section and is concentrated in the wine head and middle front section wine, and the ethyl caproate content in the middle rear section wine and the tail wine is lower, which is also one of important factors restricting the quality improvement of the white spirit.
Therefore, how to improve the content of ethyl caproate in the middle-later-stage wine and the tail wine, improve the yield of white spirit, and solve the pollution problem caused by brewing byproducts is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide an enrichment method of caproic acid in brewing byproducts and application thereof; the enrichment method can efficiently enrich the caproic acid in the brewing byproducts, improves the concentration of the caproic acid, and is favorable for esterification of the caproic acid; not only solves the problem of emission of brewing byproducts, but also can be recycled and used for supplementing ester substances in the middle-back stage wine to obtain the high-concentration ethyl caproate high-ester flavoring wine; improving the quality of white spirit.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for enriching hexanoic acid in a brew byproduct, the enrichment method comprising the steps of:
adsorbing, washing and eluting caproic acid in the brewing byproducts by adopting a chromatographic column to obtain high-concentration eluent; the chromatographic column comprises macroporous adsorption resin; the eluent adopted by the elution comprises ethanol solution; the high-concentration eluent is ethanol solution of caproic acid.
In the invention, the macroporous adsorption resin is adopted to adsorb the caproic acid in the brewing byproducts, and then the processes of washing, eluting by taking the ethanol solution as the eluent and the like are carried out to enrich and separate the caproic acid in the brewing byproducts, and the original solvent system is replaced, so that the concentration of the caproic acid is improved, the esterification reaction of the next step is facilitated, and the esterification efficiency is improved; not only solves the problem of emission of brewing byproducts, but also can be recycled, supplements esters in the middle and rear stage wine, and improves the quality of white spirit; the method provided by the invention is a method for enriching caproic acid in the brewing byproducts, and does not adsorb other acids in the brewing byproducts, such as acetic acid, lactic acid, propionic acid and the like; also, the acid enrichment methods of other areas of the prior art are not suitable for enrichment of caproic acid in the brewing byproducts.
Preferably, the concentration of the caproic acid in the brewing byproducts is 0.2-2 g/L, for example, 0.2g/L, 0.4g/L, 0.6g/L, 0.7g/L, 0.8g/L, 0.9g/L, 1g/L, 1.2g/L, 1.4g/L, 1.6g/L, 1.8g/L, 2g/L and the like.
Preferably, the pH of the brewing byproducts is 2-5, for example, 2, 3, 4, 5, etc.
Preferably, the concentration of the caproic acid in the high-concentration eluent is 15-50 g/L, and for example, 15g/L, 20g/L, 22g/L, 25g/L, 28g/L, 30g/L, 32g/L, 36g/L, 38g/L, 40g/L, 41g/L, 42g/L, 43g/L, 44g/L, 45g/L, 46g/L, 47g/L, 48g/L, 49g/L, 50g/L, etc. can be used.
Preferably, the macroporous adsorption resin comprises any one of polar macroporous resin, nonpolar macroporous resin, medium-polar macroporous resin or weak-polar macroporous resin.
Preferably, the macroporous adsorbent resin comprises any one of DZ-50, D101, HPD100, HPD400, HPD600, HPD722 or AB-8.
In the invention, DZ-50, D101 and HPD100 are nonpolar macroporous resin; HPD400 is medium-polarity macroporous resin; HPD600 is polar macroporous resin; HPD722 and AB-8 are weak polar macroporous resin.
The macroporous adsorption resin is prepared by soaking the macroporous adsorption resin in ethanol for 1-3 hours to remove impurities on the surface of the resin, loading the resin into a low-pressure chromatographic column by a wet method, washing the chromatographic column with soft water until the ethanol content of effluent liquid is below 10%, and loading samples.
Preferably, the loading flow rate during adsorption is 0.5-3 BV/h, for example, 0.5BV/h, 0.6BV/h, 0.7BV/h, 0.8BV/h, 0.9BV/h, 1BV/h, 1.1BV/h, 1.2BV/h, 1.3BV/h, 1.4BV/h, 1.5BV/h, 1.6BV/h, 1.7BV/h, 1.8BV/h, 1.9BV/h, 2BV/h, 2.1BV/h, 2.2BV/h, 2.3BV/h, 2.4BV/h, 2.5BV/h, 2.6BV/h, 2.7BV/h, 2.8BV/h, 2.9BV/h, 3BV/h, etc.; preferably 1-2 BV/h.
Preferably, the loading volume during adsorption is 25-50 BV, for example, 25BV, 26BV, 28BV, 30BV, 32BV, 34BV, 36BV, 38BV, 40BV, 42BV, 44BV, 46BV, 48BV, 50BV, etc.
In the invention, the enrichment comprises pumping brewing byproducts into a chromatographic column by adopting a pump, and loading the samples for adsorption; the loading flow rate and the volume both refer to the flow rate and the volume of the brewing byproducts; the loading flow rate and the loading volume are not within the above-defined ranges, which may result in low adsorption efficiency of the resin.
Preferably, the washed solution comprises water.
Preferably, the water comprises soft water.
Preferably, the volume of water at the time of washing is 0.5-1.5 BV, for example, 0.5BV, 0.55BV, 0.6BV, 0.65BV, 0.7BV, 0.75BV, 0.8BV, 0.85BV, 0.9BV, 0.95BV, 1BV, 1.05BV, 1.1BV, 1.15BV, 1.2BV, 1.25BV, 1.3BV, 1.35BV, 1.4BV, 1.45BV, 1.5BV, etc.; the flow rate of water is 1-2 BV/h, and may be, for example, 1BV/h, 1.1BV/h, 1.2BV/h, 1.3BV/h, 1.4BV/h, 1.5BV/h, 1.6BV/h, 1.7BV/h, 1.8BV/h, 1.9BV/h, 2BV/h, etc.
In the invention, during the washing, the volume and the flow rate of water are in the above-defined range, so that the cleaning effect is better; too small volume and incomplete cleaning; excessive volume can result in caproic acid loss; more preferably 1BV.
Preferably, the ethanol solution comprises food grade alcohol.
Preferably, the ethanol solution comprises food grade corn alcohol.
Preferably, the mass concentration of the ethanol solution is not less than 70%, for example, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 90%, 92%, 95%, 96%, 97%, 98%, 99%, 100% or the like.
In the invention, the higher the alcohol degree, namely the higher the mass concentration of the solution B, the stronger the eluting capability, the smaller the required volume, and the higher the caproic acid content in the obtained high-concentration eluent.
Preferably, the volume of the eluent is 1.5-2 BV, for example, 1.5BV, 1.6BV, 1.7BV, 1.8BV, 1.9BV, 2BV, etc.
Preferably, the flow rate of the eluent is 1.5-3 BV/h, and can be, for example, 1.5BV/h, 1.6BV/h, 1.7BV/h, 1.8BV/h, 1.9BV/h, 2BV/h, 2.1BV/h, 2.2BV/h, 2.3BV/h, 2.4BV/h, 2.5BV/h, 2.6BV/h, 2.7BV/h, 2.8BV/h, 2.9BV/h, 3BV/h, etc.
Preferably, the brew by-product comprises acid water.
Preferably, the eluting further comprises a step of washing the chromatographic column after completion of the eluting.
Preferably, the cleaning solvent comprises water.
Preferably, the flow rate of the cleaning is 2-4 BV/h, and can be, for example, 2BV/h, 2.2BV/h, 2.4BV/h, 2.6BV/h, 2.8BV/h, 3BV/h, 3.1BV/h, 3.2BV/h, 3.3BV/h, 3.4BV/h, 3.5BV/h, 3.6BV/h, 3.7BV/h, 3.8BV/h, 3.9BV/h, 4BV/h, etc.
Preferably, the wash to effluent has an alcoholicity of < 10%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc.
In the present invention, the purpose of the washing is to replace the solvent system in the column and recover ethanol from the column.
As a preferable technical scheme of the invention, the enrichment method specifically comprises the following steps:
adopting a chromatographic column filled with macroporous adsorption resin, adsorbing caproic acid with the concentration of 0.2-2 g/L in a brewing byproduct by using water at the sample loading flow rate of 0.5-3 BV/h and the sample loading volume of 25-50 BV, and washing the chromatographic column by using water with the volume of 0.5-1.5 BV and the flow rate of 1-2 BV/h; then eluting with ethanol solution with mass concentration not less than 70%, wherein the volume of the ethanol solution is 1.5-2 BV, the flow rate of the ethanol solution is 1.5-3 BV/h, and the ethanol solution of caproic acid with caproic acid concentration of 15-50 g/L is obtained.
In a second aspect, the present invention provides the use of an enrichment method according to the first aspect for enriching hexanoic acid in brewing byproducts.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the beneficial effects that:
the enrichment method of the caproic acid in the brewing byproducts provided by the invention adopts macroporous adsorption resin to adsorb the caproic acid in the brewing byproducts, and then the caproic acid in the brewing byproducts is replaced by washing, eluting and other processes, so that the concentration of the caproic acid is improved by replacing a high-concentration caproic acid and ethanol system from a low-concentration caproic acid and water system, the esterification reaction of the next step is facilitated, the esterification efficiency is improved, the problem of the emission of the brewing byproducts is solved, the recycling is also realized, the ester substances in the middle and later stage of wine are supplemented, and the quality and quality of the white wine are improved.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The macroporous adsorption resin is prepared by soaking the macroporous adsorption resin in ethanol for 2 hours to remove impurities on the surface of the resin, loading the resin into a low-pressure chromatographic column by a wet method, washing the chromatographic column with soft water until the ethanol content of effluent liquid is below 10%, and loading samples.
Example 1
The embodiment provides a method for enriching caproic acid in brewing byproduct acid water, which specifically comprises the following steps:
(1) Pumping the acid water (caproic acid concentration is 0.81g/L and volume is 25 BV) which is a by-product of brewing into a chromatographic column (which is filled with AB-8 macroporous adsorption resin, the resin dosage is 100 mL) for adsorption, and the loading flow rate is 1.5BV/h;
(2) After the step (1) is finished, adopting soft water to clean the chromatographic column, wherein the volume of the soft water is 1BV, and the flow rate of the water is 1.5BV/h;
(3) After the step (2) is finished, eluting by adopting food-grade corn alcohol with the mass concentration of more than or equal to 95%, wherein the volume of the eluent is 1.5BV, the flow rate of the eluent is 1.5BV/h, and the caproic acid-ethanol solution with the caproic acid concentration of 30.94g/L is obtained;
(4) After the step (3) is completed, the solvent system in the chromatographic column is replaced by water washing, the flow rate of the water washing is 3BV/h, the ethanol in the chromatographic column is recovered after the ethanol content in the effluent liquid is less than 10%.
Example 2
The embodiment provides a method for enriching caproic acid in brewing byproduct acid water, which specifically comprises the following steps:
(1) Pumping brewing byproduct acid water (the concentration of caproic acid is 0.79g/L, the volume is 30 BV) into a chromatographic column (filled with HPD722 macroporous adsorption resin, the resin dosage is 100 mL) for adsorption, and the loading flow rate is 1.8BV/h;
(2) After the step (1) is finished, adopting soft water to clean the chromatographic column, wherein the volume of the soft water is 1BV, and the flow rate of the water is 1.8BV/h;
(3) After the step (2) is finished, eluting by adopting food-grade corn alcohol with the mass concentration of more than or equal to 95%, wherein the volume of the eluent is 1.6BV, the flow rate of the eluent is 1.7BV/h, and the caproic acid-ethanol solution with the caproic acid concentration of 35.86g/L is obtained;
(4) After the step (3) is completed, the solvent system in the chromatographic column is replaced by water washing, the flow rate of the water washing is 3.5BV/h, the ethanol in the chromatographic column is recovered after the ethanol content in the effluent liquid is less than 10%.
Example 3
The embodiment provides a method for enriching caproic acid in brewing byproduct acid water, which specifically comprises the following steps:
(1) Pumping the acid water (caproic acid concentration is 0.84g/L, volume is 50 BV) which is a by-product of brewing into a chromatographic column (filled with D101 macroporous adsorption resin, resin dosage is 100 mL) for adsorption, and loading flow rate is 1.2BV/h;
(2) After the step (1) is finished, adopting soft water to clean the chromatographic column, wherein the volume of the soft water is 1BV, and the flow rate of the water is 1.4BV/h;
(3) After the step (2) is finished, eluting by adopting food-grade corn alcohol with the mass concentration of more than or equal to 95%, wherein the volume of the eluent is 1.8BV, the flow rate of the eluent is 1.8BV/h, and the caproic acid-ethanol solution with the caproic acid concentration of 37.62g/L is obtained;
(4) After the step (3) is completed, the solvent system in the chromatographic column is replaced by water washing, the flow rate of the water washing is 2.5BV/h, the ethanol in the chromatographic column is recovered after the ethanol content in the effluent liquid is less than 10%.
Example 4
The embodiment provides a method for enriching caproic acid in brewing byproduct acid water, which specifically comprises the following steps:
(1) Pumping the acid water (caproic acid concentration is 0.75g/L volume is 25 BV) which is a by-product of brewing into a chromatographic column (filled with AB-8 macroporous adsorption resin, the resin consumption is 100mL for enrichment, and the loading flow rate is 2BV/h;
(2) After the step (1) is finished, adopting soft water to clean the chromatographic column, wherein the volume of the soft water is 1.2BV, and the flow rate of the water is 2BV/h;
(3) After the step (2) is finished, eluting by adopting food-grade corn alcohol with the mass concentration of more than or equal to 95%, wherein the volume of the eluent is 2BV, the flow rate of the eluent is 2.5BV/h, and a caproic acid-ethanol solution with the concentration of 20.76g/L is obtained;
(4) After the step (3) is completed, the solvent system in the chromatographic column is replaced by water washing, the flow rate of the water washing is 3BV/h, the ethanol in the chromatographic column is recovered after the ethanol content in the effluent liquid is less than 10%.
Example 5
The present embodiment provides a method for enriching caproic acid in acid water as a byproduct of brewing, which is different from embodiment 1 only in that the filling resin is HPD100 macroporous adsorption resin, and other steps and parameters are the same as embodiment 1; the ethanol solution of caproic acid with the concentration of 29g/L is obtained.
Example 6
The present example provides a method for enriching caproic acid in acid water as a by-product of brewing, which is different from example 1 only in that the sample loading flow rate in step (1) is 3BV/h, and other steps and parameters are the same as those in example 1; an ethanol solution of caproic acid of a concentration of 29.08g/L was obtained.
Example 7
The present example provides a method for enriching caproic acid in acid water as a by-product of brewing, which is different from example 1 only in that the sample loading flow rate in step (1) is 0.5BV/h, and other steps and parameters are the same as those in example 1; an ethanol solution having a concentration of 27.62g/L of hexanoic acid was obtained.
Example 8
The present example provides a method for enriching caproic acid in acid water as a by-product of brewing, which is different from example 1 only in that the eluent in step (3) has a volume of 2.5BV, and other steps and parameters are the same as those in example 1; an ethanol solution having a concentration of 16.9g/L hexanoic acid was obtained.
Example 9
The present example provides a method for enriching caproic acid in acid water as a by-product of brewing, which is different from example 1 only in that the eluent in step (3) is 75% ethanol, and other steps and parameters are the same as those in example 1; an ethanol solution of hexanoic acid was obtained at a concentration of 29.77 g/L.
The concentration of the caproic acid is tested by adopting gas chromatography, and the specific parameters are as follows:
chromatographic column: agilent J & W GC Columns, CP-Wax 57CB, column length: 50m, inside diameter: 0.25mm, film thickness 0.2 μm;
column temperature: the initial temperature is 45 ℃, kept for 8min, the temperature is increased to 130 ℃ at 4 ℃/min, the temperature is increased to 200 ℃ at 20 ℃/min, and the temperature is kept for 15min;
detector temperature: 250 ℃;
sample inlet temperature: 200 ℃;
carrier gas flow rate: nitrogen gas 0.8mL/min;
sample injection amount: 0.5. Mu.L;
split ratio: 40:1;
air flow rate: 400mL/min;
hydrogen flow rate: 30mL/min.
In the invention, when the elution is carried out in the step (3) of all the embodiments, the volume of the eluent is divided into three parts, and the first third of the eluent is used for replacing the water in the chromatographic column in the step (2); the middle third is used for eluting caproic acid, and the part of eluent is collected to obtain ethanol solution of high-concentration caproic acid; illustratively, taking example 1 as an example, during elution, discarding the eluent of the previous 0.5BV, and collecting the eluent of the next 0.5BV to obtain a caproic acid-ethanol solution with the caproic acid concentration of 30.94 g/L; the caproic acid can be efficiently enriched by adopting a small amount of eluent.
Recovery of caproic acid = (volume of caproic acid concentration obtained)/(volume of acid stock caproic acid concentration) 100%.
The specific test results are shown in table 1:
TABLE 1
As can be seen from the table, the enrichment method of the caproic acid in the brewing byproducts provided by the invention adopts macroporous adsorption resin to adsorb the caproic acid in the brewing byproducts, then the caproic acid in the brewing byproducts is replaced by mutual cooperation of various technological parameters, so that the concentration of the caproic acid is improved to 16.9-37.62 g/L from 0.2-2 g/L, the recovery rate of the caproic acid is high, the alcoholic solution of the caproic acid is directly obtained, the esterification reaction of the next step is facilitated, the esterification efficiency is improved, the emission problem of the brewing byproducts is solved, the recycling is also realized, and the quality and quality of white spirit are improved in the middle and rear stage of liquor are supplemented; and has excellent enrichment effect on different brewing byproducts, such as acid water and yellow water biological fermentation liquor.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (10)
1. A method for enriching caproic acid in a brewing byproduct, which is characterized by comprising the following steps:
adsorbing, washing and eluting caproic acid in the brewing byproducts by adopting a chromatographic column to obtain high-concentration eluent;
the chromatographic column comprises macroporous adsorption resin;
the eluent adopted by the elution comprises ethanol solution;
the high-concentration eluent is ethanol solution of caproic acid.
2. The enrichment method according to claim 1, wherein the concentration of caproic acid in the brewing by-product is 0.2-2 g/L;
preferably, the pH value of the brewing byproduct is 2-5;
preferably, the concentration of the caproic acid in the high-concentration eluent is 15-50 g/L.
3. The enrichment method according to claim 1 or 2, wherein the macroporous adsorption resin comprises any one of a polar macroporous resin, a nonpolar macroporous resin, a medium-polar macroporous resin or a weak-polar macroporous resin;
preferably, the macroporous adsorbent resin comprises any one of DZ-50, D101, HPD100, HPD400, HPD600, HPD722 or AB-8.
4. A process according to any one of claims 1 to 3, wherein the loading flow rate at adsorption is 0.5 to 3BV/h, preferably 1 to 2BV/h;
preferably, the loading volume during adsorption is 25-50 BV.
5. The enrichment method according to any of claims 1-4, wherein the washed solution comprises water;
preferably, the water comprises soft water;
preferably, the volume of water is 0.5-1.5 BV during the washing;
preferably, the flow rate of the water is 0.5 to 2BV/h, and more preferably 1 to 2BV/h.
6. The enrichment method according to any of claims 1-5, wherein the ethanol solution comprises food grade alcohol;
preferably, the ethanol solution comprises food grade corn alcohol;
preferably, the mass concentration of the ethanol solution is more than or equal to 70 percent.
7. The enrichment method according to any of claims 1-6, wherein the volume of the eluent is 1.5-2 BV;
preferably, the flow rate of the eluent is 1.5-3 BV/h;
preferably, the brew by-product comprises acid water.
8. The enrichment method according to any of claims 1-7, further comprising a step of washing the chromatography column after the elution is completed;
preferably, the cleaning solvent comprises water;
preferably, the flow rate of the water during cleaning is 2-4 BV/h;
preferably, the washing is carried out until the ethanol mass percentage in the effluent is less than 10%.
9. The enrichment method according to any of claims 1-8, wherein the enrichment method comprises in particular the steps of:
adopting a chromatographic column filled with macroporous adsorption resin, adsorbing caproic acid with the concentration of 0.2-2 g/L in a brewing byproduct by using water at the sample loading flow rate of 0.5-3 BV/h and the sample loading volume of 25-50 BV, and washing the chromatographic column by using water with the volume of 0.5-1.5 BV and the flow rate of 1-2 BV/h; then eluting with ethanol solution with mass concentration not less than 70%, wherein the volume of the ethanol solution is 1.5-2 BV, the flow rate of the ethanol solution is 1.5-3 BV/h, and the ethanol solution of caproic acid with caproic acid concentration of 15-50 g/L is obtained.
10. Use of an enrichment method according to any of claims 1-9 for enriching hexanoic acid in brewing byproducts.
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