CN109337936A - Association fibre element Ethanol Method - Google Patents
Association fibre element Ethanol Method Download PDFInfo
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- CN109337936A CN109337936A CN201811274362.4A CN201811274362A CN109337936A CN 109337936 A CN109337936 A CN 109337936A CN 201811274362 A CN201811274362 A CN 201811274362A CN 109337936 A CN109337936 A CN 109337936A
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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
- C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
- C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 provides association fibre element Ethanol Methods, it comprises the following steps: 1) weighing a certain amount of cellulosic material, then vapour cooking 5-20min after crushing is added the 3-5 times of water measured and is uniformly mixed, the alkali of cellulosic material quality 1-4% or the dilute sulfuric acid of 1-5 ‰ is added；2) by basic materials thermophilic digestion 15-45min obtained by step 1), then logical oxygen 10-30min, is added the 3-5 times of water measured after filtering, and adding acid for adjusting pH is 4.5-5.5；3) by acid material thermophilic digestion 5-20min obtained by step 1), PH is measured by PH and is adjusted to 4.5-5.5；4) cellulase that enzymatic activity is 10000U is added into raw material obtained by step 2) or step 3), it is subsequently introduced the hermetically sealed can inside holding 24-48h that temperature is 55 DEG C, is cooled to 35 DEG C, 1-4% is added in the thermotolerant yeast of cellulosic material quality, heat-preservation fermentation 7 days to get；Cellulosic structure is destroyed using cooking process in the present invention, reduces the murder by poisoning to cellulase and saccharomycete, biogas fermentation technology is introduced and enough thermal energy and electric energy is provided, improve comprehensive utilization ratio and economic benefit.
Description
Technical field
The present invention relates to ethyl alcohol preparation technical fields, and in particular to association fibre element Ethanol Method.
Background technique
Cellulose (cellulose) be by glucose group at macromolecular polysaccharide.Not soluble in water and common organic solvents.It is
The main component of plant cell wall.Cellulose is that a kind of most wide, content is most polysaccharide is distributed in nature, accounts for plant kingdom's carbon and contains
50% or more of amount.The content of cellulose of cotton is close to 100%, for natural most pure cellulose source.In general timber, fiber
Element accounts for 40~50%, and there are also 10~30% hemicellulose and 20~30% lignin.
Ethyl alcohol is produced since raw material sources are extensive, cheap by raw material of cellulose, and prospect extensively expands.Cellulose it is main
Composition is cellulose, hemicellulose and lignin.The former two can be hydrolyzed to monosaccharide, then fermented generation ethyl alcohol.Lignin
Cannot hydrolyze and form protective layer around cellulose influences cellulose hydrolysis.
With the gradual depletion of fossil energy, phenomena such as consuming climate warming, environmental degradation brought by fossil energy
Occur, a kind of substitute of reproducible clean energy resource as fossil energy is found in the urgent hope of people, is meeting consumption need
The destruction to environment is reduced while asking.Alcohol fuel is as a kind of reproducible clean energy resource, from 1970s in beauty
State, Brazil start to carry out, and are raw material since most of the alcohol fuel initially carried out is by corn and other starches matter cereal crops,
The rise for leading to world food price forms the situation that grain is striven with people, constrains its large-scale promotion.With cellulase skill
The development of art, the exploitation of cellulosic ethanol technology and cellulase, which are commercially produced, just gradually to make good and scale.
It discloses in patent document CN103060391A disclosed in the China and goes out suitable for the low temperature of cellulosic ethanol production
Bacterium method, the low temperature sterilization method the following steps are included: (1) weigh it is quantitative by pretreated cellulosic material and culture medium
Other components be directly added into fermentor；(2) quantitative cellulase enzyme solution is added according to final fermentation volume and be warming up to
50~65 DEG C, 1~3h is kept the temperature, the fermentation temperature of alcohol fermentation bacterial strain is cooled to；(3) culture is added by way of aseptic inoculation
Good alcohol fermentation bacterial strain seed suspension maintains tank to be pressed in 0.01~0.02Mpa, and it is straight to control suitable condition progress anaerobic fermentation
To fermentation ends.The low temperature sterilization method eliminates tradition in the catalytic efficiency for guaranteeing to take into account cellulase while not contaminating miscellaneous bacteria
The inhibition product that sterilization method generates reduces energy consumption and utilizes, and saves sterilizing cost.
But there are high production cost, heavy-polluted defects for existing association fibre element Ethanol Method.
Summary of the invention
Aiming at the problems existing in the prior art, it the present invention provides association fibre element Ethanol Method, effectively compensates for
Defect of the existing technology.
In order to achieve the above object, the present invention is achieved by the following technical programs:
A kind of association fibre element Ethanol Method, the association fibre element Ethanol Method comprise the following steps:
1) a certain amount of cellulosic material is weighed, then the 3-5 times of water measured mixing is added in vapour cooking 5-20min after crushing
Uniformly, the alkali of cellulosic material quality 1-4% or the dilute sulfuric acid of 1-5 ‰ is added；
2) by basic materials thermophilic digestion 15-45min obtained by step 1), then logical oxygen 10-30min, is added 3-5 after filtering
The water of amount again, adding acid for adjusting pH is 4.5-5.5；
3) by acid material thermophilic digestion 5-20min obtained by step 1), PH is measured by PH and is adjusted to 4.5-5.5；
4) cellulase that enzymatic activity is 10000U is added into raw material obtained by step 2) or step 3), is subsequently introduced temperature
For in 55 DEG C of sealing bucket, 24-48h is kept the temperature, is cooled to 35 DEG C, 1-4% is added in the thermotolerant yeast of cellulosic material quality,
Heat-preservation fermentation 7 days to get.
Preferably, cellulosic material is careless class or one kind of the wooden class in the step 1).
Preferably, the alkali in the step 1) in alkali process is sodium hydroxide.
Careless type high temp boiling temperature is 160 DEG C, and the wooden type high temp boiling temperature is 180 DEG C
Preferably, the acid in the step 2) is dilute sulfuric acid.
Preferably, thermotolerant yeast is Angel thermotolerant yeast in the step 3).
Preferably, the dosage of the step 4) cellulase is the 1-4% of cellulosic material quality.
The beneficial effects of the present invention are:
The present invention is the combination of a variety of methods, and alkali-diluted acid method, boiling-alkaline process, boiling-alkali oxygen method, steams alkali oxygen-diluted acid method
Boil-diluted acid method, boiling-alkali-diluted acid method, boiling-alkali oxygen-diluted acid method.It can according to the local situation or soda acid price determines
Application method.
Independent or 2 kinds of methods are combined the destruction that can be completed to raw material mix to the present invention in fact, improve cellulose
Transformation efficiency, know so being desirable to extract more valuable byproducts, improving using the methods of using boiling-alkali-diluted acid
Economic benefit reduces or spends the murder by poisoning of absolute cellulase and saccharomycete, improves conversion ratio.
It is specific:
1) ethyl alcohol is produced since raw material sources are extensive, cheap by raw material of cellulose, prospect extensively expands；
2) cooking process destroys cellulosic structure and sterilizing and provides original for cellulase manufacturing shop and saccharomycete workshop
Material reduces production cost, improves benefit；
3) alkaline process or alkali oxygen method will not participate in reaction and influence the lignin hydrolyzed and largely remove in advance, and this method alkali is used
Amount reduces 1 times or more than alkaline pulp-making, and digestion time shortens 3-4 times, and, less energy consumption smaller to environment, atmosphere pollution does not need multiple
Miscellaneous alkali recovery process；
4) diluted acid method removes partial lignin and hemicellulose, when combining with alkaline process or alkali oxygen method, most of removal half
Cellulose, sour dosage is few, pollutes small；
5) raw material sources of the present invention are extensive, cheap, without geographical restrictions, can promote on a large scale, heavy industrialization
Production can also small-scale workshop-based production.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of creative work.
Embodiment 1:
A kind of association fibre element Ethanol Method, comprises the following steps:
1) a certain amount of careless class, vapour cooking 5min after crushing are weighed, the water that 5 times of amounts are then added is uniformly mixed, is added fine
Tie up the sodium hydroxide of plain material quality 1% or 5 ‰ dilute sulfuric acid；
2) by basic materials thermophilic digestion 15min obtained by step 1), then logical oxygen 30min, is added 3 times of amounts after filtering
Water, adding acid for adjusting pH is 5.5；
3) by acid material boiling 5min under the conditions of 160 DEG C obtained by step 1), PH is measured by PH and is adjusted to 5.5；
4) it is the fiber that 10000U mass is careless class quality 1% that enzymatic activity is added into raw material obtained by step 2) or step 3)
Plain enzyme is subsequently introduced in the sealing bucket that temperature is 55 DEG C, keeps the temperature 48h, is cooled to 35 DEG C, is added 1% in cellulosic material quality
Angel thermotolerant yeast, heat-preservation fermentation 7 days to get.
Embodiment 2:
A kind of association fibre element Ethanol Method, comprises the following steps:
1) a certain amount of wooden class, vapour cooking 20min after crushing are weighed, the water that 3 times of amounts are then added is uniformly mixed, is added fine
Tie up the sodium hydroxide of plain material quality 4% or 1 ‰ dilute sulfuric acid；
2) by basic materials boiling 45min under the conditions of 180 DEG C obtained by step 1), then logical oxygen 10min, is added after filtering
The water of 5 times of amounts, adding acid for adjusting pH is 4.5；
3) by acid material thermophilic digestion 20min obtained by step 1), PH is measured by PH and is adjusted to 4.5；
4) it is the fiber that 10000U mass is careless class quality 4% that enzymatic activity is added into raw material obtained by step 2) or step 3)
Plain enzyme is subsequently introduced in the sealing bucket that temperature is 55 DEG C, and heat preservation for 24 hours, is cooled to 35 DEG C, is added 4% in cellulosic material quality
Angel thermotolerant yeast, heat-preservation fermentation 7 days to get.
Embodiment 3:
A kind of association fibre element Ethanol Method, comprises the following steps:
1) a certain amount of careless class, vapour cooking 5min after crushing are weighed, the water that 5 times of amounts are then added is uniformly mixed, is added fine
Tie up the sodium hydroxide of plain material quality 1% or 5 ‰ dilute sulfuric acid；
2) by basic materials temperature boiling 15min under the conditions of 160 DEG C obtained by step 1), then logical oxygen 10min, adds after filtering
The water for entering 5 times of amounts, adding acid for adjusting pH is 4.5；
3) by acid material thermophilic digestion 20min obtained by step 1), PH is measured by PH and is adjusted to 4.5；
4) it is the fiber that 10000U mass is careless class quality 4% that enzymatic activity is added into raw material obtained by step 2) or step 3)
Plain enzyme is subsequently introduced in the sealing bucket that temperature is 55 DEG C, and heat preservation for 24 hours, is cooled to 35 DEG C, is added 4% in cellulosic material quality
Angel thermotolerant yeast, heat-preservation fermentation 7 days to get.
Embodiment 4:
A kind of association fibre element Ethanol Method, comprises the following steps:
1) a certain amount of wooden class, vapour cooking 5min after crushing are weighed, the water that 4 times of amounts are then added is uniformly mixed, is added fine
Tie up the sodium hydroxide of plain material quality 2% or 3 ‰ dilute sulfuric acid；
2) by basic materials thermophilic digestion 20min obtained by step 1), then logical oxygen 20min, is added 4 times of amounts after filtering
Water, adding acid for adjusting pH is 4.5；
3) by acid material boiling 10min under the conditions of 180 DEG C obtained by step 1), PH is measured by PH and is adjusted to 5；
4) it is the fiber that 10000U mass is the wooden class quality 3% that enzymatic activity is added into raw material obtained by step 2) or step 3)
Plain enzyme is subsequently introduced in the sealing bucket that temperature is 55 DEG C, keeps the temperature 36h, is cooled to 35 DEG C, is added 2% in cellulosic material quality
Angel thermotolerant yeast, heat-preservation fermentation 7 days to get.
Embodiment 5:
A kind of association fibre element Ethanol Method, comprises the following steps:
1) a certain amount of careless class is weighed, then vapour cooking 10min after crushing is added the 3-5 times of water measured and is uniformly mixed, is added
The sodium hydroxide of cellulosic material quality 3% or 3 ‰ dilute sulfuric acid；
2) by basic materials boiling 20min under the conditions of 160 DEG C obtained by step 1), then logical oxygen 20min, is added after filtering
The water of 4 times of amounts, adding acid for adjusting pH is 5；
3) by acid material thermophilic digestion 4min obtained by step 1), PH is measured by PH and is adjusted to 5；
4) it is the fiber that 10000U mass is careless class quality 3% that enzymatic activity is added into raw material obtained by step 2) or step 3)
Plain enzyme is subsequently introduced in the sealing bucket that temperature is 55 DEG C, keeps the temperature 48h, is cooled to 35 DEG C, is added 1% in cellulosic material quality
Angel thermotolerant yeast, heat-preservation fermentation 7 days to get.
Embodiment 6
Certain content of starting materials is weighed after pulverizer crushes, a part removes marsh-gas fermentation tank, and biogas is removed through biogas purifier
The sundries such as sulphur and water go gas fired-boiler output steam to provide thermal energy for system, and large-scale production high steam drives large-scale generator
Group, small-scale production drive biogas generator, provide electric energy for system, extra biogas is made into liquefied gas sale.Overflowing liquid as
Plant culture, into water culture garden.Plant culture is done together through filter press filters pressing, filtrate and overflowing liquid after bottom material fermentation
It uses, filtration cakes torrefaction rear portion is granulated through pelletizer and uses as fertilizer and feed, and a part is used as mushroom culture medium.
The storage after the granulation of biomass granulation machine of raw material a part is sold as biomass fuel.
A part of raw material enters the directly logical steam of the horizontal-type evaporator less than or equal to 160 DEG C and heats careless class, keeps the temperature 5-
20min, waste heat recycles after heat preservation.Enter cellulase manufacturing shop and ferment after agitated machine adds water (solid-liquid ratio 1: 2) to stir again
Female bacterium fermentation plant is added water, black liquor and washing lotion (solid-liquid ratio 1: 3-5) and enters alkali oxygen cooker, is added by lye metering pump former
Expect the alkali (NaoH) of 2-8%, careless class 2-4%, the wooden class 4-8%.Lead to vapour heating to 160 DEG C, keeps the temperature 15-45min.After heat preservation
Stopping heating natural cooling waste heat recycling, is down to 130 DEG C or less and the open sky of oxygen is led to by air compressor machine, pressure is less than or equal to 0.7Mpa,
100 DEG C of oxygen feeding stops, oxygen supply time cannot be below 30min.(lignin removing rate should be 70% for content of lignin in analysis lye
More than).
After entering filter press filters pressing after the completion of boiling, black liquor enters Black Liquor Concentration tank and leads to steam heating waste heat recycling, when reaching
To after proper viscosity, into filter press filters pressing, filtrate enters black liquor recovery tank, and black material a part goes to make brick field and cement and raw material
Large-scale particle is made through pelletizer in crushed material brickmaking together, remaining black material, carries out high temperature cabonization, tar recycling, and carbonized particles are done
For fuel use.Alkaline waste water goes to biodegradable pond.
Filters pressing raw material go blender to add water and stir after again after filter press filters pressing, filtrate removes washing lotion storage tank.After raw material filters pressing
Agitated machine enters diluted acid cooker after adding water (solid-liquid ratio 1: 3-5) to stir, and the sulphur of total amount 1-5 ‰ is added by diluted acid metering pump
Acid leads to steam heating (160 DEG C of careless class, wooden 180 DEG C of the class), keeps the temperature 5-20min, waste heat recycling.It has surplus heat and enters flash tank
The sundries such as furfural and organic acid are removed, bottom liquid is again introduced into filter press filters pressing.Filtrate enters xylose storage tank, and the agitated machine of filter cake is again
Enzymatic vessel is removed after secondary plus water (solid-liquid ratio 1: 3-5) stirring, after Ph value is adjusted to 4.5-5.5 by diluted acid metering pump, adds raw material 1-4%
Acidic cellulase is heated to 55 DEG C of heat preservation 24-48h.Raw material 1-4% thermotolerant yeast is added into combined ferment tank to be heated to
35 DEG C, 3d is kept the temperature, 30 DEG C is down to and leads to a small amount of air thermal preservation 3d.Bottom liquid follows together with the overflowing liquid of overflow tank into vacuum through filters pressing
Ring opens vacuum cycle machine operation 15-30min, and Extract enters crude glycol tank, and clear liquid and the agitated machine of filter cake stir back joint hair
Fermentation tank circulating fermentation.Acid waste water goes to biodegradable pond.
It has surplus heat and flash tank is gone to lead to high steam, removed the impurity such as furfural, organic acid using flash tank, through cooling
Device enters sundries tank, and after condensed water analysis is without impurity such as furfurals, removing deoxygenation case is boiler water supply.
Experimental result: alcohol content is 2 ‰ in thermophilic digestion 2h fermentation liquid, and thermophilic digestion 4h alcohol content is 4 ‰, high temperature
It is 8-12 ‰ that boiling 8h, which leads to oxygen 10min alcohol content, and 110 DEG C of boiling 8h lead to oxygen 10min alcohol content 12-16 ‰, 120 DEG C of boilings
8h leads to oxygen 10min alcohol content 14-18 ‰, and 120 DEG C of steaming 2h of corn ear boil 8h alcohol content 18-24 ‰, 120 DEG C of boilings of sawdust
12h leads to oxygen 10min alcohol content 12-18 ‰, secondary fermentation alcohol content 12-20 ‰ (self-control leavening).
According to paper-making pulping process experience: under certain conditions of cooking, when paper pulp yield and content of lignin change little,
Digestion time shortens with the raising of boiling temperature, every to increase 10 DEG C of digestion times shortening half.In digestion time and other steamings
Boil condition it is identical when, content of lignin is lower in the higher slurry of boiling temperature.Cellulose ethanol content is generally in 20-40g/L, originally
Ethyl alcohol highest content 24g/L is tested to reach minimum standard.It is effective according to experiment and paper-making pulping process empirical evidence this method.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or
Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (7)
1. a kind of association fibre element Ethanol Method, which is characterized in that comprise the following steps:
1) a certain amount of cellulosic material is weighed, then vapour cooking 5-20min after crushing is added the 3-5 times of water measured and is uniformly mixed,
The alkali of cellulosic material quality 1-4% or the dilute sulfuric acid of 1-5 ‰ is added；
2) by basic materials thermophilic digestion 15-45min obtained by step 1), then logical oxygen 10-30min, is added 3-5 times after filtering and measures
Water, add acid for adjusting pH be 4.5-5.5；
3) by acid material thermophilic digestion 5-20min obtained by step 1), PH is measured by PH and is adjusted to 4.5-5.5；
4) cellulase that enzymatic activity is 10000U is added into raw material obtained by step 2) or step 3), being subsequently introduced temperature is 55
DEG C sealing bucket in, keep the temperature 24-48h, be cooled to 35 DEG C, 1-4% is added in the thermotolerant yeast of cellulosic material quality, heat preservation
Fermentation 7 days to get.
2. association fibre element Ethanol Method according to claim 1, which is characterized in that cellulosic material in the step 1)
For careless class or one kind of the wooden class.
3. association fibre element Ethanol Method according to claim 1, which is characterized in that in the step 1) in alkali process
Alkali is sodium hydroxide.
4. association fibre element Ethanol Method according to claim 2, which is characterized in that careless type high temp boiling temperature is 160
DEG C, the wooden type high temp boiling temperature is 180 DEG C.
5. association fibre element Ethanol Method according to claim 1, which is characterized in that the acid in the step 2) is dilute sulphur
Acid.
6. association fibre element Ethanol Method according to claim 1, which is characterized in that thermotolerant yeast in the step 3)
For Angel thermotolerant yeast.
7. association fibre element Ethanol Method according to claim 1, which is characterized in that the step 4) cellulase
Dosage is the 1-4% of cellulosic material quality.
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| CN201811274362.4A CN109337936A (en) | 2018-10-30 | 2018-10-30 | Association fibre element Ethanol Method |
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