CN102115764B - Method for producing alcohol by taking anaerobic effluent as ingredient water - Google Patents
Method for producing alcohol by taking anaerobic effluent as ingredient water Download PDFInfo
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- CN102115764B CN102115764B CN2010105764117A CN201010576411A CN102115764B CN 102115764 B CN102115764 B CN 102115764B CN 2010105764117 A CN2010105764117 A CN 2010105764117A CN 201010576411 A CN201010576411 A CN 201010576411A CN 102115764 B CN102115764 B CN 102115764B
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Abstract
The invention relates to a method of an alcohol production process in which anaerobic effluent is taken as ingredient water. The method comprises the following steps of: mixing raw materials with deaminized anaerobic effluent in a specified material to water ratio; adjusting pH value and adding liquefied enzyme, heating, digesting and liquefying; cooling, and adding saccharified enzyme for saccharifying; lowering the temperature, inoculating and fermenting; distilling; precipitating sulfate radicals before performing anaerobic treatment on the distilled effluent obtained by distilling; and performing anaerobic treatment on the distilled effluent, and performing deamination treatment to obtain ingredient water for fermenting a next batch of alcohol. By adopting method, the running stability of the process in which the anaerobic effluent is taken as the ingredient water is enhanced, the content of hydrogen sulfide in marsh gas obtained by fermenting anaerobic marsh gas is lowered, and subsequent use of the marsh gas is facilitated.
Description
Technical field
The present invention relates to a kind of alcohol producing process take anaerobic effluent as ingredient water, specifically mainly refer to the method by calcium precipitation and removal of ammonia and nitrogen, sulfate radical and the ammonia nitrogen that affects the process stabilizing operation removed, belong to the fermented food industry technical field.
Background technology
Produce in the technique of alcohol in traditional liquid state fermentation, size mixing by water through pulverizing, adding for starchy material, cooking and liquefaction and saccharification, then inoculation yeast bacterium fermentation.When adopting saccharine material, only need suitably dilution to ferment by the inoculation yeast bacterium.When producing 1 ton of alcohol, can produce the slops of 12-15 ton.Slops has the characteristics such as temperature high (approximately 95 ℃), acid (about pH 4) and COD high (COD 80000-120000mg/L), has brought serious pollution hidden trouble, has become the bottleneck problem that the restriction alcohol industry further develops.
The treatment process of existing alcohol distillation waste liquid mainly contains: the concentrate drying method is produced DDGS, anaerobism one aerobe facture and slops reuse etc.But these methods are difficult to accomplish taking into account of environmental benefit and economic benefit.If slops is passed through first anaerobic treatment, when then anaerobic effluent being carried out reuse, then can obtain simultaneously good economic benefit and social benefit.But can have two main problems when adopting anaerobic effluent to carry out reuse: 1, the pH of anaerobic effluent is usually at 7.0-8.2, and usually needs control pH about 4.0 during zymamsis, therefore needs to add sulfuric acid and regulates.And contain the ammonia nitrogen of high density in the anaerobic effluent, have very strong surge capability, when regulating pH, when needing a large amount of sulfuric acid, its sulfuric acid addition to be the tap water batching more than 10 times.Increased like this production cost of alcohol, and sulfate radical can be reduced to hydrogen sulfide in marsh gas fermentation processes, be unfavorable for the later use of biogas.In addition, sulfide also can produce harm to zymamsis.2, it is relatively poor that anaerobic system is removed the ability of nitrogen, and when adopting anaerobic effluent to prepare burden, along with the increase of circulation batch, the ammonia nitrogen in the system can produce accumulation.And the accumulation meeting of ammonia nitrogen brings harm to biogas fermentation and zymamsis, and then technique can not be moved steadily in the long term.
Summary of the invention
The object of the invention is to overcome the weak point when adopting anaerobic effluent to carry out zymamsis, thus set up a kind of can steady running, can obtain simultaneously the method for the zymamsis of good social effect and environmental benefit.
A kind of alcohol producing process take anaerobic effluent as ingredient water of the present invention, adopt following processing step:
1, batching: the starchy material after will pulverizing mixes with anaerobic effluent behind the last consignment of removal of ammonia and nitrogen, and the mass ratio of starchy material and anaerobic effluent is 1: 1.5-5, the employing tap water is supplied during the anaerobic effluent deficiency.
Raw material mainly refers to the starchiness materials such as cassava (doing), Ipomoea batatas (doing), corn, Chinese sorghum, rice, starch.
2, liquefaction: between 5.8-6.5, interpolation commodity α-amylase is hot digestion then, makes starch liquefacation with the pH of the feed liquid that obtains in acid or the alkali set-up procedure 1.
Liquefaction belongs to maturation process, and kind and the addition of α-amylase are unrestricted, and boiling temperature and cooking time depend on kind and the addition of α-amylase, so boiling temperature and cooking time are unrestricted.
Regulate the used acid of material liquid pH and refer to the mineral acids such as sulfuric acid, hydrochloric acid, phosphoric acid, used alkali refers to sodium hydroxide, yellow soda ash, sodium bicarbonate etc.With one or more compound uses wherein.
3, saccharification: liquefaction cools 58-65 ℃ with liquefied fermented glutinous rice after finishing.Then adjust the pH value of liquefier with acid, add saccharifying enzyme and carry out saccharification, saccharification time is 0-60 minute.
Saccharification belongs to maturation process, and the kind of saccharifying enzyme, addition and pH are unrestricted.
Saccharification time selects end value namely to represent not saccharification in 0 minute, the gained liquefied fermented glutinous rice directly is cooled to the temperature of requirement in the step 4 in the step 2, adjust the pH of liquefier to the best pH of saccharifying enzyme effect with mineral acid described in the step 2 or alkali again, then add saccharifying enzyme, enter step 4 and ferment.
4, fermentation: the gained feed liquid further is cooled to 28-32 ℃ in the step 3, the cultured yeast saccharomyces cerevisiae seed liquor of the 6-15% of access material liquid volume, or directly add Active Dry Yeast according to the addition of 0.01-1.0g/L, and to ferment, the controlled fermentation temperature is between 28-38 ℃.
Before the fermentation, can add urea or the ammonium sulfate of 0-20g/L in the fermented liquid, and the potassium primary phosphate of 0-2.0g/L and 0-2.0g/L sal epsom.
5, distillation: the fermented liquid of fermentation finished thoroughly1 is distilled, obtain alcohol.
Distil process belongs to maturation process, and concrete distillation condition is unrestricted.
6, remove sulfate radical: add the calcium salt of 0.01-0.1mol/L in the alcohol distillation waste liquid that obtains in the step 5, make the sulfate radical precipitation in the alcohol distillation waste liquid.
The used calcium salt of precipitated sulfur acid group refers to calcium hydroxide, calcium oxide, calcium chloride etc.With one or more compound uses wherein.
7, the slops in the step 6 is added in the anaerobic reactor, carry out biogas fermentation.
8, ammonia nitrogen removal: add alkali in the anaerobic effluent that obtains through the anaerobic methane fermentation in the step 7, regulate the pH to 8.5-10.5 of anaerobic effluent, then carry out ammonia nitrogen removal;
The ammonia nitrogen removal method mainly contains two kinds of boiling denitrogenation and vacuum denitrifications
During the boiling deamination, boiling temperature is 100 ℃, and the time is 0.5-3 hour;
During vacuum deamination, absolute pressure is 0.05-90KPa, and temperature is 20-80 ℃, and the deamination time does not require.
The alkali that uses during deamination refers to calcium hydroxide, calcium oxide, sodium hydroxide etc.With one or more compound uses wherein.
9, the ammonia nitrogen removal anaerobic effluent that obtains of step 8 is got back to step 1, successively circulation.
Compared with the prior art the present invention has the following advantages:
1, before slops enters the anaerobic methane fermentation, make the sulfate radical precipitation by the method for adding calcium salt, eliminated the potential hazard of sulfate radical to the anaerobic methane fermentation, improved the stability of anaerobic methane fermentation;
2, the removal of sulfate radical greatly reduces the concentration of hydrogen sulfide in the biogas that obtains after the anaerobic methane fermentation, has reduced the corrosion to equipment when burning of hydrogen sulfide containing biogas;
3, the removal of sulfate radical greatly reduces the concentration of hydrogen sulfide in the anaerobic effluent that obtains after the anaerobic methane fermentation, has eliminated the inhibition of hydrogen sulfide to zymamsis;
4, before preparing burden anaerobic effluent is carried out deamination and process, the nitrogen content that can be used in the ingredient water of each batch zymamsis keeps stable, is conducive to suitability for industrialized production;
When 5, the anaerobic effluent behind the employing ammonia nitrogen removal carried out zymamsis as ingredient water, the nitrogen content in the slops that obtains reduced greatly, was conducive to follow-up anaerobic methane fermentation and kept stably operation.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
Following the present invention is further described in connection with the embodiment in the accompanying drawing:
Embodiment one: a kind of alcohol producing process take anaerobic effluent as ingredient water, adopt following processing step:
1, gets Tapioca Starch 100g, add the upper crowd anaerobic effluent 200g that processes through step 8 and prepare burden;
2, with 30% (w/w) sulfuric acid with the feed adjustment pH to 6.0 that obtains in the step 1, add the high temperature resistant α-amylase of 800u, in 100 ℃ of lower boilings 30 minutes, make starch liquefacation;
3, after liquefaction finishes, liquefied fermented glutinous rice is cooled 60 ℃, then use 30% (w/w) sulfuric acid that the pH of feed liquid is adjusted to 4.0, then add the 12000u saccharifying enzyme and carried out saccharification 30 minutes;
4, gained feed liquid in the step 3 further is cooled to 30 ℃, 15% cultured yeast saccharomyces cerevisiae seed liquor of access material liquid volume is fermented, and 30 ℃ of leavening temperatures, fermentation time are 60 hours;
5, the fermented liquid with fermentation finished thoroughly1 distills, and obtains product alcohol and slops;
6, according to the concentration of sulfate radical in the alcohol distillation waste liquid that obtains in the step 5, add calcium hydroxide, make the sulfate radical precipitation in the alcohol distillation waste liquid complete;
7, will add anaerobic reactor through the slops that step 6 is processed and carry out biogas fermentation;
8, add calcium hydroxide in the anaerobic effluent that obtains to step 7, regulate the pH to 10.5 of anaerobic effluent, deamination was carried out in boiling in 3 hours under 100 ℃ of conditions.
9, the deamination anaerobic effluent that obtains of step 8 is got back to step 1.
Embodiment two: a kind of alcohol producing process take anaerobic effluent as ingredient water, adopt following processing step:
1, gets Tapioca Starch 100g, add the upper crowd anaerobic effluent 300g that processes through step 8 and prepare burden;
2, with 30% (w/w) sulfuric acid with the feed adjustment pH to 6.0 that obtains in the step 1, add the high temperature resistant α-amylase of 1000u, in 100 ℃ of lower boilings 30 minutes, make starch liquefacation;
3, after liquefaction finishes, liquefied fermented glutinous rice is cooled 60 ℃, then use 30% (w/w) sulfuric acid that the pH of feed liquid is adjusted to 5.0, then add the 13000u saccharifying enzyme and carried out saccharification 15 minutes;
4, gained feed liquid in the step 3 further is cooled to 30 ℃, 8% cultured yeast saccharomyces cerevisiae seed liquor of access material liquid volume is fermented, and 30 ℃ of leavening temperatures, fermentation time are 40 hours;
5, the fermented liquid with fermentation finished thoroughly1 distills, and obtains product alcohol and slops;
6, according to the concentration of sulfate radical in the alcohol distillation waste liquid that obtains in the step 5, add calcium oxide, make the sulfate radical precipitation in the alcohol distillation waste liquid complete;
7, the slops in the step 6 is added in the anaerobic reactor, carry out biogas fermentation;
8, add calcium oxide in the anaerobic effluent that obtains to step 7, regulate the pH to 8.5 of anaerobic effluent, deamination was carried out in boiling in 5 hours under 100 ℃ of conditions.
9, the deamination anaerobic effluent that obtains of step 8 is got back to step 1.
Embodiment three: a kind of alcohol producing process take anaerobic effluent as ingredient water, adopt following processing step:
1, gets Tapioca Starch 100g, add the upper crowd anaerobic effluent 250g that processes through step 8 and prepare burden;
2, with 30% (w/w) sulfuric acid with the feed adjustment pH to 6.0 that obtains in the step 1, add the high temperature resistant α-amylase of 800u, in 100 ℃ of lower boilings 30 minutes, make starch liquefacation;
3, after liquefaction finishes, liquefied fermented glutinous rice is cooled 60 ℃, then use 30% (w/w) sulfuric acid that the pH of feed liquid is adjusted to 5.0, then add the 12000u saccharifying enzyme and carried out saccharification 60 minutes;
4, gained feed liquid in the step 3 further is cooled to 28 ℃, adds active dry yeast 0.2g, ferment, 28 ℃ of leavening temperatures, fermentation time are 60 hours;
5, the fermented liquid with fermentation finished thoroughly1 distills, and obtains product alcohol and slops;
6, according to the concentration of sulfate radical in the alcohol distillation waste liquid that obtains in the step 5, add calcium chloride, make the sulfate radical precipitation in the alcohol distillation waste liquid complete;
7, will add anaerobic reactor through the slops that step 6 is processed and carry out biogas fermentation;
8, adding calcium hydroxide in the anaerobic effluent that obtains to step 7, regulate the pH to 9.5 of anaerobic effluent, is under the condition of 0.1KPa and 60 ℃ in absolute pressure, deamination 1 hour.
9, the deamination anaerobic effluent that obtains of step 8 is got back to step 1.
Claims (5)
1. alcohol producing process take anaerobic effluent as ingredient water, adopt following processing step:
(1), batching: the starchy material after will pulverizing mixes with anaerobic effluent behind the last consignment of removal of ammonia and nitrogen, and the mass ratio of starchy material and anaerobic effluent is 1: 1.5-5, the employing tap water is supplied during the anaerobic effluent deficiency;
(2), liquefaction: between 5.8-6.5, interpolation commodity α-amylase is hot digestion then, makes starch liquefacation with the pH of the feed liquid that obtains in acid or the alkali set-up procedure (1);
(3), saccharification: liquefaction cools 58-65 ℃ with liquefier after finishing, and then adjusts the pH value of liquefier with acid, adds saccharifying enzyme and carries out saccharification, and saccharification time is 0-60 minute;
(4), fermentation: gained feed liquid in the step (3) further is cooled to 28-32 ℃, the cultured yeast saccharomyces cerevisiae seed liquor of the 6-15% of access material liquid volume, or directly add Active Dry Yeast according to the addition of 0.01-1.0g/L, ferment, the controlled fermentation temperature is between 28-38 ℃;
(5), distillation: the fermented liquid of fermentation finished thoroughly1 is distilled, obtain alcohol;
(6), remove sulfate radical: add the calcium salt of 0.01-0.1mol/L in the alcohol distillation waste liquid that obtains in the step (5), make the sulfate radical precipitation in the alcohol distillation waste liquid;
(7), the slops in the step (6) is added in the anaerobic reactor, carry out biogas fermentation;
(8), ammonia nitrogen removal: in the middle anaerobic effluent that obtains through the anaerobic methane fermentation of step (7), add alkali, regulate the pH to 8.5-10.5 of anaerobic effluent, then carry out ammonia nitrogen removal;
(9), the ammonia nitrogen removal anaerobic effluent that obtains of step (8), get back to step 1, successively circulation.
2. a kind of alcohol producing process take anaerobic effluent as ingredient water according to claim 1, it is characterized in that: described raw material refers to cassava, Ipomoea batatas, corn, Chinese sorghum, rice, starch.
3. a kind of alcohol producing process take anaerobic effluent as ingredient water according to claim 1 is characterized in that the used calcium salt of precipitated sulfur acid group refers to calcium hydroxide, calcium oxide, calcium chloride, with one or more compound uses wherein.
4. a kind of alcohol producing process take anaerobic effluent as ingredient water according to claim 1, the alkali that uses when it is characterized in that deamination refers to calcium hydroxide, calcium oxide, sodium hydroxide, with one or more compound uses wherein.
5. a kind of alcohol producing process take anaerobic effluent as ingredient water according to claim 1, when it is characterized in that deamination, with the pH regulator of anaerobic effluent to 8.5-10.5, come removal of ammonia and nitrogen by the method for boiling or vacuum outgas.
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| CN102424462A (en) * | 2011-09-01 | 2012-04-25 | 泸州品创科技有限公司 | Pretreatment method of wine brewing waste water |
| CN102503019B (en) * | 2011-10-12 | 2013-10-16 | 江南大学 | Method for realizing biogas slurry reutilization by recycling biogas slurry |
| CN102775022B (en) * | 2012-07-30 | 2014-10-29 | 广西轻工业科学技术研究院 | Treating and recycling method for mixed effluent of cassava alcohol |
| CN103382490B (en) * | 2013-08-08 | 2015-06-10 | 河南天冠企业集团有限公司 | Method for fermenting alcohol by reusing alcohol grain liquid and medium-temperature anaerobic effluent |
| CN106591379B (en) * | 2016-12-02 | 2020-08-04 | 江南大学 | Alcohol production method based on comprehensive utilization of wastewater |
| CN106755128A (en) * | 2016-12-02 | 2017-05-31 | 江南大学 | A kind of reuse of anaerobic digestion solution part as Alcohol Production spice water method |
| CN106995825A (en) * | 2017-06-05 | 2017-08-01 | 江南大学 | A kind of aerobic sigestion effluent reuse is in the technique of alcoholic fermentation |
| CN109081512B (en) * | 2018-08-31 | 2021-06-01 | 广州中康食品有限公司 | high-COD value syrup recycling treatment process |
| CN111254166A (en) * | 2018-11-30 | 2020-06-09 | 国投生物科技投资有限公司 | Method for co-producing alcohol and biogas by utilizing cassava and method for generating power by utilizing biogas |
| CN110981099A (en) * | 2019-12-18 | 2020-04-10 | 江南大学 | Method for producing ethanol by recycling biogas slurry and vinasse clear liquid and reusing |
| CN113943758B (en) * | 2020-07-16 | 2024-01-16 | 中粮生物科技股份有限公司 | Method for producing ethanol |
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| CN1286982C (en) * | 2004-12-08 | 2006-11-29 | 江南大学 | Closed cycle technique for producing alcohol in high concentration through fermentation of clear solution |
| CN101880692A (en) * | 2010-07-06 | 2010-11-10 | 江南大学 | Alcohol fermentation method capable of improving raw material utilization rate |
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