CN107142286A - The method that aflatoxin is removed in alcohol production process - Google Patents
The method that aflatoxin is removed in alcohol production process Download PDFInfo
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- CN107142286A CN107142286A CN201710447234.4A CN201710447234A CN107142286A CN 107142286 A CN107142286 A CN 107142286A CN 201710447234 A CN201710447234 A CN 201710447234A CN 107142286 A CN107142286 A CN 107142286A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The present invention relates to Alcohol Production field, a kind of method that aflatoxin is removed in alcohol production process is disclosed, this method introduces montmorillonite during being included in biomass material fermenting and producing alcohol, wherein, the particle diameter of the montmorillonite is below 850 μm.By above-mentioned technical proposal, the present invention realizes effective removing of aflatoxin in alcohol production process in the case where ensureing product (alcohol grain) characteristic, simple to operate, is adapted to industrial production application.
Description
Technical field
The present invention relates to Alcohol Production field, and in particular to the method that aflatoxin is removed in alcohol production process.
Background technology
Aflatoxin (Aflatoxin, AFT) is the toxicant that a class has strong carcinogenicity and strong inhibitive ability of immunity.
It is that a class is mycetogenetic secondary by aspergillus flavus (Aspergillus flavus), aspergillus parasiticus (A.parasiticus) etc.
Metabolite.It is present in soil, animals and plants, various nuts, is particularly easy to pollution peanut, corn, rice, soybean, wheat
Deng grain oil product, the class mycotoxin for be mycotoxin Poisoning maximum, extremely protruding human health risk.Due to fungi
The special construction of toxin, the general acid-base value (pH3-7) of their high temperature resistants, tolerance, the process of the various physics of tolerance.Huang Qu
Mould toxin is general relatively to be stablized in neutral solution, but is slightly decomposed in strongly acidic solution, is divided in pH9-10 strong base solution
Solution is rapid, and the decomposition temperature of high temperature resistant aflatoxin B1 is 268 DEG C.
Biomass to alcohol conversion process generally comprises that raw material is crushed, sized mixing, liquefying, being saccharified, fermenting, distilling, vinasse are dried, final production
Product are alcohol and alcohol grain.In alcoholic fermentation process, aflatoxin is easily enriched in alcohol grain, so as to influence alcohol grain
Further utilization.
Conventional poison-removing method has Physical (extrusion cooking method, gamma-rays method), chemical method (ammonia process, sodium sulfite at present
Method, sodium-hypochlorite process, hydrogen peroxide method, Ozone) and bioanalysis (enzyme process, microbial method).And in alcohol production process, it is yellow
The removal methods of aspertoxin mainly have Ozone, ammoniation process and microbial method.
(McKENZIE KS, SARR AB, MAYURA K, the et al.Oxidative degradation such as McKenzie
and detoxification of mycotoxins using a nova source of ozone[J].Food and
Chemical Toxicology,1997,35(8):807-820) contain aflatoxin with 20% (w/w) ozone continuous processing
The corn slurry of standard items, the corn slurry of the aflatoxins containing rice and each 5min of aflatoxin standard solution, it is as a result yellow
Aspertoxin B1 degradation rate is respectively 71.8%, 66.9% and 100%.This ozone treating process is simple, pollution-free, without residual
Stay, but in large-scale production and application, the ozone for how continuously preparing a large amount of high concentrations is a challenge.
Northern US research center (NRRC) completes by the experiment of four-stage and utilizes aspergillus flavus in ammonia degrading maize
Pilot process research (BREKKE OL, PEPLINSKI AJ, NOFSINGER GW, the et al.Aflatoxin of plain toxin
inactivation in com by ammonia gas:A field trial[J].Trans.ASAE,1979,22:425-
432):Corn and ammonia are sealed in 13d in warehouse at normal temperatures, aflatoxin content is degraded to 20 μ g/ from 1000 μ g/kg
Below kg.There is certain potential safety hazard in this ammoniated treatment method, and need to carry out the system reform to existing storage facilities,
Management difficulty is big, therefore is also difficult to apply in production practices.
It can be seen that, there is poor operability (must be carried out under the conditions of extreme temperature and pressure) in Ozone and ammoniation process, no
Safety (toxic residua is formed), the high defect of cost.Microbial method is comparatively safe, but industrial strain transformation is difficult, fragile
Nutrition, sense organ and functional characteristic of bad product etc..
The content of the invention
The problem of being damaged the invention aims to the poor operability and properties of product for overcoming prior art presence, carries
Method for removing aflatoxin in alcohol production process.
Montmorillonite also known as montmorillonite, are the layer minerals being made up of the superfine hydrous alumino silicates of particle, after water suction
Expansion, volume increases several times greater to more than ten times, and it can be used safely in feed.The present inventor has found under study for action,
Montmorillonite is added in alcohol production process can effectively remove aflatoxin, it can also be ensured that the properties of alcohol grain.
Therefore, to achieve these goals, the invention provides a kind of method that aflatoxin is removed in alcohol production process, the party
Method introduces montmorillonite during being included in biomass material fermenting and producing alcohol, wherein, the particle diameter of the montmorillonite is 850
Below μm.
By above-mentioned technical proposal, the present invention realizes Alcohol Production mistake in the case where ensureing product (alcohol grain) characteristic
Effective removing of (particularly with biomass material fermenting and producing alcohol during) aflatoxin, simple to operate in journey, fits
Close industrial production application.
Embodiment
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
In the present invention, in the case where not making opposite explanation, the weight of raw material is in terms of butt (including embodiment);Make
Term " montmorillonite " refers to octahedra montmorillonite product, belongs to a kind of alumino-silicate;The sieve pair that " particle diameter " is passed through with particle
The mesh size answered is characterized;Defined according to GB 8275-2009:1g solid enzyme powders (or 1ml liquid enzymes), in 70 DEG C, pH=6.0
Under the conditions of, the enzyme amount in 1min required for liquefaction 1mg soluble starches, as 1 enzyme activity unit, with u/g (or u/ml) table
Show, enzyme activity unit continues to use this definition in the present invention.
The method of removing aflatoxin is included in the alcohol production process that the present invention is provided is fermented with biomass material
Montmorillonite is introduced during production alcohol, wherein, the particle diameter of the montmorillonite is below 850 μm, preferably below 45 μm, more
It is preferred that in 0.2-45 μ ms.
As long as the montmorillonite that specified particle diameter is used in alcohol production process is that the purpose of the present invention can be achieved, to montmorillonite
Consumption do not require that under preferable case, relative to the biomass material per ton in terms of butt, the montmorillonite is used particularly
Measure as 1-180kg, most preferably more preferably 1-15kg, 4.5-9kg.
In the present invention, the specific opportunity for introducing montmorillonite is not required particularly, can be any in production process
Period.Specifically, following steps (carrying out successively) are generally included with the process of biomass material fermenting and producing alcohol:
Step A:The pretreatment of biomass material;
Step B:Size mixing;
Step C:Liquefaction;
The step D optionally carried out:Saccharification;
Step E:Fermentation;
Step F:Distillation;
Step G:Dry;
And the montmorillonite can be introduced in step A-G at least one (particularly at least one of step B-F).For
The further removal effect for improving aflatoxin, and influence reduction by montmorillonite to index of fermenting is to the limit,
It is preferred that introducing montmorillonite in step E.In practical operation, if adding montmorillonite in multiple steps, the use of montmorillonite
Gross weight in amount expression gross weight, namely each step is preferably within the above range.
Wherein, the pretreatment of the biomass material can include raw material crushing, and the particle diameter through raw material crushing rear material is excellent
It is selected in 1.25-4000 μ ms, more preferably in 500-3000 μ ms.If former using cellulose raw material as biomass
Material, can also carry out steam blasting, boiling etc. to it.
It can be sized mixing according to conventional condition.Preferably, the condition sized mixing includes:Material-water ratio (i.e. biomass material
Weight ratio between water) 1:1-100, more preferably 1:1.5-4.The temperature sized mixing can be 20-100 DEG C, preferably 45-65
℃.The pH sized mixing can be 2-8, preferably 5-7.
Method and condition that the method and condition for being liquefied and being saccharified can be well known to those skilled in the art.It is excellent
Selection of land, liquefied temperature is 55-105 DEG C, more preferably 80-105 DEG C.Liquefied pH is preferably 2-8, more preferably 4-7.Liquefaction
Time be preferably 0.1-48h, more preferably 1-8h.Enzyme used in liquefaction and saccharification can also be conventional selection, herein not
Repeat again.
Preferably, the temperature of saccharification is 20-80 DEG C, more preferably 45-70 DEG C.The pH of saccharification is preferably 2-8, more preferably
3-5.The time of saccharification is preferably 0-48h, more preferably 0-8h.Saccharification is the step of selectivity is carried out, namely will can be liquefied
Product is directly used in fermentation, liquefaction products can also be used further to fermentation after saccharification, those skilled in the art can be according to reality
Border situation determines whether to carry out.When being saccharified, the time of saccharification is generally in more than 20min.
Fermentation can also be carried out conventionally with condition, it is preferable that the condition of fermentation includes:Strain inoculum concentration
(in terms of cell butt) 0.1-5kg/t biomass materials.The pH of fermentation is preferably 2-8, more preferably 3-6.The temperature of fermentation is excellent
Elect 10-60 DEG C, more preferably 25-40 DEG C as.The time of fermentation is preferably 0.1-20 days, more preferably 1-5 days.The mode of fermentation
It can be batch fermentation, continuously ferment or semicontinuous fermentation.Can be fermented monose such as glucose and/or fructose, oligosaccharides such as sucrose
And/or the microorganism fungus kind (such as yeast) of galactolipin may be used to the fermentation process of the present invention, because saccharomyces cerevisiae is to make
The microorganism for the zymohexose that commonly used ethanol-tolerant, accessory substance are few on liquor industry, alcohol yied is high, therefore institute of preferably fermenting
The strain used is saccharomyces cerevisiae (Saccharomyces cerevisiae).
By coordinate it is above-mentioned it is preferred size mixing, liquefy, be saccharified and fermentation condition, can more effectively remove aspergillus flavus poison
Element, while ensureing the yield of alcohol and the characteristic of alcohol grain.
Wherein it is possible to go out alcohol by separated, then by molecular sieve dehydration, absolute alcohol is made.
Bottoms after distillation obtains alcohol grain after drying, for example, solid-liquid point can be carried out to bottoms by press filtration
From liquid phase is concentrated, and dries filter residue, and alcohol grain is obtained after mixing.
In the present invention, the biomass material can be conventional selection, for example, can selected from corn, rice, wheat,
The starch materials such as sorghum, potato, sweet potato, jerusalem artichoke, cassava, the carbohydrate such as sugar-cane juice, molasses, sorgo juice, beet juice, syrup, with
And the cellulose raw material such as straw, straw, maize straw, energy grass.
The present invention will be described in detail by way of examples below.
In following examples, montmorillonite is purchased from Inner Mongol Ai Mu Chemical Co., Ltd.s;The analysis of aflatoxin B1 content
Method is aflatoxin B1 competitive ELISA RNA isolation kit, and purchased from U.S. HELICA, article No. is 941BAFL011-96;Alcohol
The constituent analysis reference standard GB/T 25866-2010 of grain are carried out.
Embodiment 1
Step A:Corn flour (raw material) is crushed, and crushing rear material particle footpath is 500-3000 μm;
Step B:Size mixing, material-water ratio 1:2.2, temperature 60 C, pH5.6;
Step C:Liquefaction, using the Thermostable α-Amylase purchased from Novozymes Company, consumption is 25 enzyme activity units/g former
Material, 90 DEG C of temperature, pH6, time 5h;
Step D:Saccharification, using 4060 compounded saccharifying enzymes produced purchased from Genencor Company, consumption be 50 enzyme activity units/
G raw materials, temperature 60 C, pH4, time 1h;
Step E:Fermentation, strain is the super highly active dry yeast of Angel, purchased from Hubei Angel Yeast joint-stock company, bacterium
Plant inoculum concentration 1kg/t raw materials, pH4,33 DEG C of temperature, 5 days time;
Step F:Distillation, alcohol is gone out by three-tower differential pressure separated, then by molecular sieve dehydration (140 DEG C, 200kPa),
Absolute alcohol is made, and calculates yield, as a result as shown in table 1;
Step G:Dry, the bottoms distilled by press filtration carries out separation of solid and liquid, and clear liquid is concentrated, dry filter residue, mixing
Alcohol grain is made afterwards, alcohol grain constituent analysis is subjected to, as a result as shown in table 1;
Wherein, the montmorillonite of 9kg/t raw materials is added in step E (particle diameter is below 45 μm).
Embodiment 2
Step A:Wheat flour (raw material) is crushed, and crushing rear material particle footpath is 1000-2500 μm;
Step B:Size mixing, material-water ratio 1:1.5, temperature 45 C, pH7;
Step C:Liquefaction, using the Thermostable α-Amylase purchased from Novozymes Company, consumption is 30 enzyme activity units/g former
Material, 80 DEG C of temperature, pH4, time 8h;
Step D:Saccharification, using 4060 compounded saccharifying enzymes produced purchased from Genencor Company, consumption be 25 enzyme activity units/
G raw materials, temperature 45 C, pH3, time 8h;
Step E:Fermentation, strain is the super highly active dry yeast of Angel, purchased from Hubei Angel Yeast joint-stock company, bacterium
Plant inoculum concentration 0.1kg/t raw materials, pH3,25 DEG C of temperature, 3 days time;
Step F:Distillation, alcohol is gone out by three-tower differential pressure separated, then by molecular sieve dehydration (140 DEG C, 200kPa),
Absolute alcohol is made, and calculates yield, as a result as shown in table 1;
Step G:Dry, the bottoms distilled by press filtration carries out separation of solid and liquid, and clear liquid is concentrated, dry filter residue, mixing
Alcohol grain is made afterwards, alcohol grain constituent analysis is subjected to, as a result as shown in table 1;
Wherein, the montmorillonite of 9kg/t raw materials is added in stepb (particle diameter is below 45 μm).
Embodiment 3
Step A:Sweet potato flour (raw material) is crushed, and crushing rear material particle footpath is 1200-2000 μm;
Step B:Size mixing, material-water ratio 1:4,65 DEG C of temperature, pH6;
Step C:Liquefaction, using the Thermostable α-Amylase purchased from Novozymes Company, consumption is 35 enzyme activity units/g former
Material, 105 DEG C of temperature, pH7, time 1h;
Step D:Saccharification, using 4060 compounded saccharifying enzymes produced purchased from Genencor Company, consumption be 10 enzyme activity units/
G raw materials, temperature 70 C, pH5, time 5h;
Step E:Fermentation, strain is the super highly active dry yeast of Angel, purchased from Hubei Angel Yeast joint-stock company, bacterium
Plant inoculum concentration 3kg/t raw materials, pH6,40 DEG C of temperature, 1 day time;
Step F:Distillation, alcohol is gone out by three-tower differential pressure separated, then by molecular sieve dehydration (140 DEG C, 200kPa),
Absolute alcohol is made, and calculates yield, as a result as shown in table 1;
Step G:Dry, the bottoms distilled by press filtration carries out separation of solid and liquid, and clear liquid is concentrated, dry filter residue, mixing
Alcohol grain is made afterwards, alcohol grain constituent analysis is subjected to, as a result as shown in table 1;
Wherein, the montmorillonite of 4.5kg/t raw materials is separately added into step B and E (particle diameter is below 45 μm).
Embodiment 4
Alcohol is produced according to the method for embodiment 1, unlike, the amount of the montmorillonite of addition is 0.5kg/t raw materials, as a result
As shown in table 1.
Embodiment 5
Alcohol is produced according to the method for embodiment 1, unlike, the amount of the montmorillonite of addition is 180kg/t raw materials, as a result
As shown in table 1.
Embodiment 6
Alcohol is produced according to the method for embodiment 1, unlike, montmorillonite is added in step G, as a result as shown in table 1.
Embodiment 7
Alcohol is produced according to the method for embodiment 1, unlike, montmorillonite is added in step, as a result as shown in table 1.
Comparative example 1
Alcohol is produced according to the method for embodiment 1, unlike, montmorillonite is added without, as a result as shown in table 1.
Comparative example 2
According to embodiment 1 method produce alcohol, unlike, the particle diameter of the montmorillonite of addition in 45-60 μ ms,
As a result it is as shown in table 1.
Table 1
Note:Ppb represents weight concentration, 1ppb=1ng/g.
Can be seen that by the result of table 1 can effectively remove the Huang during production alcohol using the method for the present invention
Aspertoxin, and will not significantly influence the yield of alcohol.Comparing embodiment 1 and embodiment 4-7 can be seen that according to preferred
Mode, which adds montmorillonite, has substantially preferably detoxification efficiency.
The preferred embodiment of the present invention described in detail above, still, the present invention is not limited thereto.In the skill of the present invention
In art concept, technical scheme can be carried out a variety of simple variants, including each technical characteristic with it is any its
Its suitable method is combined, and these simple variants and combination should equally be considered as content disclosed in this invention, belong to
Protection scope of the present invention.
Claims (8)
1. the method for aflatoxin is removed in a kind of alcohol production process, it is characterised in that this method is included in biomass
Montmorillonite is introduced during fermenting raw materials production alcohol, wherein, the particle diameter of the montmorillonite is below 850 μm.
2. according to the method described in claim 1, wherein, the particle diameter of the montmorillonite is below 45 μm.
3. method according to claim 1 or 2, wherein, relative to the biomass material per ton in terms of butt, the illiteracy
De- stone consumption is 1-180kg.
4. method according to claim 1 or 2, wherein, relative to the biomass material per ton in terms of butt, the illiteracy
De- stone consumption is 1-15kg.
5. according to the method described in claim 1, wherein, following step is included with the process of biomass material fermenting and producing alcohol
Suddenly:
Step A:The pretreatment of biomass material;
Step B:Size mixing;
Step C:Liquefaction;
The step D optionally carried out:Saccharification;
Step E:Fermentation;
Step F:Distillation;
Step G:Dry;
And the montmorillonite is introduced at least one of step A-G.
6. method according to claim 5, wherein, the montmorillonite is introduced at least one of step B-F.
7. the method according to claim 5 or 6, wherein, the pretreatment of the biomass material is crushed including raw material, through original
Expect the particle diameter of crushing rear material in 1.25-4000 μ ms;
And/or, the condition sized mixing includes:Material-water ratio 1:1-100,20-100 DEG C of temperature, pH2-8;
And/or, liquefied condition includes:55-105 DEG C of temperature, pH2-8, time 0.1-48h;
And/or, the condition of saccharification includes:20-80 DEG C of temperature, pH2-8, time 0-48h;
And/or, the condition of fermentation includes:Strain inoculum concentration 0.1-5kg/t biomass materials, pH2-8,10-60 DEG C of temperature, time
0.1-20 days.
8. the method according to claim 5 or 6, wherein, the pretreatment of the biomass material is crushed including raw material, through original
Expect the particle diameter of crushing rear material in 500-3000 μ ms;
And/or, the condition sized mixing includes:Material-water ratio 1:1.5-4,45-65 DEG C of temperature, pH5-7;
And/or, liquefied condition includes:80-105 DEG C of temperature, pH4-7, time 1-8h;
And/or, the condition of saccharification includes:45-70 DEG C of temperature, pH3-5, time 0-8h;
And/or, the condition of fermentation includes:PH3-6,25-40 DEG C of temperature, 1-5 days time.
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