CN103045659B - Method for detoxification in production of citric acid by utilizing cassava fermentation - Google Patents
Method for detoxification in production of citric acid by utilizing cassava fermentation Download PDFInfo
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- CN103045659B CN103045659B CN201210584039.3A CN201210584039A CN103045659B CN 103045659 B CN103045659 B CN 103045659B CN 201210584039 A CN201210584039 A CN 201210584039A CN 103045659 B CN103045659 B CN 103045659B
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Abstract
The invention provides a method for detoxification in production of citric acid by utilizing cassava fermentation. The method comprises steps that fresh cassava is taken as raw material, and aspergillus niger is ued for citric acid fermentation production; in the extraction process at the back of citric acid fermentation, calcium carbonate is added into the fermentation filtrate to form the citric acid calcium precipitation, and then large amount of waste liquor containing various complex enzymes is generated; the waste liquor is circularly utilized, and the waste liquor in the amount of 5-10 percent is put into the cassava raw material in the prior stewing and detoxification, so that the cooking detoxification time and temperature (the cooking time for detoxification liquefaction is shortened from the original 6 hours to 2 hours, and the cooking temperature for detoxification liquefaction is decreased from 100 DEG C to 85 DEG C) can be greatly reduced, and the energy wastage is greatly reduced. Compared with a traditional cassava detoxification method, the detoxification method provided by the invention is provided with distinct superiorities, reveals a favorable industrial application perspective, and is suitable for large-scale industrial citric acid fermentation production.
Description
Technical field
The invention belongs to fermentation engineering field, specifically, relate to a kind of poison-removing method utilizing in cassava fermentation production of citric acid.
Background technology
Citric acid is widely used in daily life, is one of biochemical product having the call in the world at present, and consumption reaches more than 1,800,000 tons every year on average.Along with the growth of global economy, domestic and international market also constantly increases the demand of citric acid.China is maximum in the world citric acid export State, and Meyer lemon acid annual capacity has exceeded 1,000,000 tons at present, accounts for 53% left and right in the world, and 2,010 850,000 tons of annual export volumes exceed the half of quantum of world trade.But for example, along with the fast development of world's Biochemical Industry (alcohol fuel), consumption and the price of the farm crop such as corn grow with each passing day, grain raw material becomes a large bottleneck of restriction citric acid production.The citric acid production technology of development non-grain raw material has become worldwide development trend, and compared with other non-grain crop, the economic benefit of cassava and social benefit are comparatively outstanding.
Cassava is one of the world's three yampi classes, and reputation claims " king of starch ", " underground grain ".Thick raw easily cultivation, strong adaptability, can on the fragmentary soil in the dysgonic nonirrigated farmland of other staple crop and limit, cultivate, obtain good output and quality, also can intercropping in young growth and opening in the ranks, or with beans, melon and gramineous crop intercropping or crop rotation, be beneficial to the exploitation of soil and human resources, important role in dry farming.China's cassava resource abundance, in line with the strategy of " non-grain is main, suits measures to local conditions ", sets up citric acid production enterprise, and utilizes aspergillus niger to carry out the full slag fermentation method of cassava and produce citric acid.In order to make the production process of citric acid more efficient, brief and economical, now need to utilize new fresh cassava directly to pulverize after for fermentation.But the cyanide content of new fresh cassava is higher, and toxicity is larger, if without detoxification process with regard to inoculation fermentation, can and produce the growth of fermentation strain aspergillus niger and acidly can have very large restraining effect.
The toxicant containing in cassava is linamarin (Linamarin) and two kinds of cyanogenic glycosides of lotaustralin (lotaustraline).First cyanogenic glycoside decomposes and generates cyanalcohol and sugar under the effect of beta-glucosidase, and cyanalcohol is very unstable, and natural decomposition is corresponding ketone, aldehyde cpd and prussic acid.Wherein prussic acid is highly toxic substance, reaches certain concentration, the respiration of meeting severe inhibition organism.The process that cyanogenic glycoside produces prussic acid is as follows:
Therefore, set up the detoxification process of efficient economy more the production of cassava citric acid is had to vital effect.For reducing the content of prussiate in cassava, utilize the better water-soluble and stronger volatile feature of prussic acid of cyanogenic glycoside, common way, for example tapioca root is cut into cassava slice, shine system about 72 hours, can make the content of HCN in cassava reduce greatly, other removal method also comprises oven drying method (70 ℃ ~ 80 ℃), water-boiling method, rinsing or sun airing etc.The now boiling methods that adopt more, although but effectively detoxification of the method, boiling time reaches nearly 8 hours can reach desirable detoxification efficiency, the energy that loss is a large amount of.
Above poison-removing method all expends a large amount of manpower and materials, is unfavorable for save energy, does not meet production requirement and the technology trends of efficient economy.
Summary of the invention
The object of this invention is to provide a kind of poison-removing method utilizing in cassava fermentation production of citric acid.
In order to realize the object of the invention, a kind of poison-removing method utilizing in cassava fermentation production of citric acid of the present invention, comprises the following steps:
1) take new fresh cassava as raw material, aspergillus niger, as fermentation strain, utilizes biological fermentation process to carry out citric acid production, removes thalline and impurity in fermented liquid, adds wherein calcium carbonate to precipitate, and reclaims filtrate and is the detoxification liquid containing prozyme;
2) take new fresh cassava as raw material, directly pulverize defibrination, add wherein step 1) containing the detoxification liquid of prozyme, then add that alpha-amylase liquefies and boiling detoxification, in the liquefied substance after detoxification, access fermentation strain, carry out citric acid fermentation production.
Aforesaid poison-removing method, step 2) in be the 5%-10% of cassava soup compound gross weight containing the addition of the detoxification liquid of prozyme, preferably 5%.
Aforesaid poison-removing method, step 2) in the addition of alpha-amylase (enzyme live 4000U/ml) be 0.3 ‰-0.8 ‰ of cassava soup compound gross weight.
Aforesaid poison-removing method, step 2) in liquefaction temperature be 80 ℃-90 ℃ (preferably 85 ℃), liquefying time is the preferred 2h of 1h-2.5h().
Aforesaid poison-removing method, step 1) and step 2) described in fermentation strain be commercially available aspergillus niger (Aspergillus niger) Co-827.
Aforesaid poison-removing method, step 1) and step 2) in the fermentative medium formula that uses when fermentation be: 15%-19% cassava, 0.3%-0.5% Zein powder, surplus is water.
Aforesaid poison-removing method, step 1) and step 2) described in fermentation condition be: 37 ℃, air flow 0.4-0.9vvm, tank pressure 0.1Mpa, dissolved oxygen is higher than 40%.
The present invention also provides a kind of detoxification liquid for new fresh cassava fermentation production of citric acid, its preparation method is: take cassava as raw material, aspergillus niger (preferably aspergillus niger Co-827) is as fermentation strain, utilize biological fermentation process to carry out citric acid production, remove thalline and impurity in fermented liquid, add wherein calcium carbonate to precipitate, reclaim filtrate and get final product.
The fermentative medium formula using when fermentation is: 15%-19% cassava, and 0.3%-0.5% Zein powder, surplus is water; Fermentation condition is: 37 ℃, and air flow 0.4-0.9vvm, tank pressure 0.1Mpa, dissolved oxygen is more than or equal to 40%.
The aspergillus niger using in the present invention is the production bacterium of plurality of enzymes, yield of enzyme is large, enzyme is complete, and there is a very strong cellulase activity, wherein beta-glucosidase can act in cassava containing cyanogen compound cyanogenic glycoside, make it finally all be converted into free prussic acid, and the boiling point of prussic acid is only 25.7 ℃, can volatilize fast by hot digestion.
The present invention is take new fresh cassava as raw material, use aspergillus niger as fermentation strain, utilize biological fermentation process to carry out the production of citric acid, then after citric acid fermentation in abstraction process, when adding calcium carbonate that citric acid is changed into after citrate of lime precipitation in fermentating liquid filtrate, can produce a large amount of waste liquids, in this waste liquid, contain multiple prozyme.This waste liquid of recycle, amount by it by 5%-10% joins in the boiling detoxification new fresh cassava raw material in early stage, wherein contained beta-glucosidase can effectively improve detoxification efficiency, and contained cellulase, can reduce to a certain extent viscosity, improve reducing sugar content, thereby (cooking time of detoxification liquefaction shortened to 2 hours by original 6 hours significantly to reduce time of boiling detoxification and temperature, the boiling temperature of detoxification liquefaction, be reduced to 85 ℃ by original 100 ℃), greatly reduce energy loss.Method of the present invention, compared with traditional cassava poison-removing method, has obvious advantage, has represented good prospects for commercial application, during the citric acid fermentation that is applicable to large-scale industrialization is produced.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that the present invention utilizes the poison-removing method in new fresh cassava fermentation production of citric acid.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.If do not specialize, the conventional means that in embodiment, technique means used is well known to those skilled in the art, the raw materials used commercial goods that is.
Embodiment 1 utilizes 10m in cassava fermentation production of citric acid
3the cultivation of seeding tank
By mixing with 44kg Zein powder (being rich in nitrogenous source, somatomedin etc. in Zein powder) after fresh 1050kg Cassava crushing defibrination, add water and size mixing, then pump into 10m
3in seeding tank, add water and be settled to 8m
3, add 3.4L alpha-amylase (enzyme 40000U/mL alive), 8.5kg calcium chloride (enzyme protective material alive), add again 425L last time to ferment to obtain containing prozyme waste liquid, (method that obtains this waste liquid is: take cassava as raw material, aspergillus niger is as fermentation strain, utilize biological fermentation process to carry out citric acid production, remove thalline and impurity in fermented liquid, add wherein calcium carbonate to precipitate, reclaim filtrate, obtain), then be warming up to 85 ℃, maintain approximately 2 hours, (every bottled liquid measure is 5L after being finally cooled to 37 ℃, to access 20 bottles of aspergillus nigers (Aspergillus niger) Co-827 wheat bran spore, spore count is 15000ml
-1), at 37 ℃, air flow is 12.75m
3/ min, cultivates under the condition of tank pressure 0.1MPa approximately 20 hours, can finish to cultivate, stand-by.
Embodiment 2 utilizes 90m in cassava fermentation production of citric acid
3the cultivation of fermentor tank
To after fresh 14400kg Cassava crushing defibrination, mix with 294kg Zein powder; add water and size mixing; then pump in 90m3 fermentor tank; add water and be settled to 71.4m3, add 30.5L alpha-amylase (enzyme 40000U/mL alive), 84kg calcium chloride (enzyme protective material alive); add again 4200L last time to ferment to obtain containing prozyme waste liquid (with the waste liquid preparation method of describing in embodiment 1); then be warming up to 85 ℃, maintain approximately 2 hours, access 8.4m after being finally cooled to 37 ℃
3the aspergillus niger seed liquor of preparation in embodiment 1, at 37 ℃, air flow is 63.75m
3/ min, cultivates under the condition of tank pressure 0.1MPa approximately 60 hours, when residual total reducing sugar is below 2%, produces acid more than 14%, can finish fermentation when transformation efficiency 85% is above.
Embodiment 3 is containing the preparation of the detoxification liquid of prozyme
First the fermented liquid obtaining after embodiment 2 fermentation ends is heated to 80 ℃, crosses while hot plate-and-frame filter press, remove by filter thalline and insoluble impurity, the content of sampling and measuring citric acid.Then, calculate the add-on of calcium carbonate according to neutralization reaction formula, can calculate 1g citric acid by reaction formula and need add 0.174g calcium carbonate, calculate thus the total amount that need add calcium carbonate.
Filtrate is preheated to 70 ℃, slowly adds while stirring calcium carbonate, heat up simultaneously, in making, reach 85 ℃, insulated and stirred 30min with the temperature of terminal.
Filtered while hot, filter cake washs repeatedly with boiling water, until sugar-free detects nondiscoloration.The filter cake obtaining is citrate of lime precipitation, and filtrate is the detoxification liquid containing prozyme, collects and pumps into storage tank, treats that earlier fermentation uses.
Embodiment 4 is the application in cassava fermentation production of citric acid containing the detoxification liquid of prozyme
New fresh cassava raw material, after pulverizing defibrination, adds the detoxification liquid containing prozyme of preparation in embodiment 3 wherein, and its addition is 8% of cassava soup compound gross weight.Then the alpha-amylase (enzyme 4000U/ml alive) that adds cassava soup compound gross weight 0.6 ‰ liquefies, and (liquefaction temperature is 85 ℃, liquefying time is 2h) and boiling detoxification, in the liquefied substance after detoxification, access aspergillus niger (Aspergillus niger) Co-827, carry out citric acid fermentation production.When residual total reducing sugar is below 2%, produce acid more than 14%, when transformation efficiency 85% is above, can finish fermentation.Fermentation condition is: 37 ℃, and air flow 0.4-0.9vvm, tank pressure 0.1Mpa, dissolved oxygen is higher than 40%.
Concrete technology flow process as shown in Figure 1.
And in the case of not adding the detoxification liquid containing prozyme, utilize 90m
3fermentor tank, carries out the fermentation of cassava citric acid, need to, by mixing with 294kg Zein powder after fresh 15200kg Cassava crushing defibrination, add water and mix well, and then pumps into 90m
3in fermentor tank, add water and be settled to 71.5m
3, adding 40.5L alpha-amylase (enzyme live in 40000U/mL), 90kg calcium chloride (enzyme live protective material), is then warming up to 95 ℃, maintains approximately 6 hours, accesses 8.5m after being finally cooled to 37 ℃
3the aspergillus niger seed liquor of preparation in embodiment 1, at 37 ℃, air flow is 64.5m
3/ min, cultivates under the condition of tank pressure 0.1MPa approximately 65 hours, when residual total reducing sugar is below 2%, produces acid more than 14%, can finish fermentation when transformation efficiency 85% is above.Result shows, drop into the amount of cassava and the enzyme amount of interpolation all than embodiment 4 height, and cooking time is longer than embodiment 4.
Adopt method of the present invention, recycle is containing the detoxification liquid of prozyme, amount by it by 5%-10% joins in the boiling detoxification cassava raw material in early stage, (cooking time of detoxification liquefaction shortened to 2 hours by original 6 hours can significantly to reduce time of boiling detoxification and temperature, the boiling temperature of detoxification liquefaction, be reduced to 85 ℃ by original 100 ℃), greatly reduce energy loss.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (3)
1. utilize the poison-removing method in cassava fermentation production of citric acid, it is characterized in that, comprise the following steps:
1) take new fresh cassava as raw material, aspergillus niger, as fermentation strain, utilizes biological fermentation process to carry out citric acid production, removes thalline and impurity in fermented liquid, adds wherein calcium carbonate to precipitate, and reclaims filtrate and is the detoxification liquid containing prozyme;
2) take new fresh cassava as raw material, directly pulverize defibrination, add wherein step 1) containing the detoxification liquid of prozyme, then add that alpha-amylase liquefies and boiling detoxification, in the liquefied substance after detoxification, access fermentation strain, carry out citric acid fermentation production;
Step 2) in be the 5%-10% of cassava soup compound gross weight containing the addition of the detoxification liquid of prozyme;
Step 2) in the addition of alpha-amylase be 0.3 ‰-0.8 ‰ of cassava soup compound gross weight, wherein the enzyme of alpha-amylase is lived as 4000U/ml;
Step 2) in liquefaction temperature be 80 ℃-90 ℃, liquefying time is 1h-2.5h;
Step 1) and step 2) described in fermentation strain be aspergillus niger (Aspergillus niger) Co-827.
2. poison-removing method according to claim 1, is characterized in that, step 1) and step 2) in when fermentation the fermentative medium formula that uses be: 15%-19% cassava, 0.3%-0.5% Zein powder, surplus is water.
3. poison-removing method according to claim 1, is characterized in that, step 1) and step 2) described in fermentation condition be: 37 ℃, air flow 0.4-0.9vvm, tank pressure 0.1Mpa, dissolved oxygen is higher than 40%.
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| CN105296549A (en) * | 2015-10-23 | 2016-02-03 | 安徽丰原发酵技术工程研究有限公司 | Method for improving citric acid fermenting level |
| CN105420290A (en) * | 2015-12-17 | 2016-03-23 | 广西中粮生物质能源有限公司 | Method for removing hydrocyanic acid in fresh cassava as raw material for preparing ethyl alcohol by fermentation method |
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| CN102443611B (en) * | 2010-10-13 | 2014-03-05 | 中粮生物化学（安徽）股份有限公司 | Production method of citric acid |
| CN102219286A (en) * | 2011-03-21 | 2011-10-19 | 安徽丰原生物化学股份有限公司 | Treatment method of wastewater generated during citric acid preparation and preparation method of citric acid |
| CN102399830A (en) * | 2011-11-02 | 2012-04-04 | 日照鲁信金禾生化有限公司 | Method for producing citric acid through complete cassava fermentation |
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