CN101487024B - Method for preparing ethanol from tuber crops raw material - Google Patents
Method for preparing ethanol from tuber crops raw material Download PDFInfo
- Publication number
- CN101487024B CN101487024B CN2008100562145A CN200810056214A CN101487024B CN 101487024 B CN101487024 B CN 101487024B CN 2008100562145 A CN2008100562145 A CN 2008100562145A CN 200810056214 A CN200810056214 A CN 200810056214A CN 101487024 B CN101487024 B CN 101487024B
- Authority
- CN
- China
- Prior art keywords
- cylinder
- raw material
- waste liquid
- enzymolysis
- potato
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses an ethanol preparation method that utilizes raw potato materials and comprises following steps: skin of the raw potato materials is peeled, the peeled raw potato materials are crashed, the crashed product is mixed with an enzyme, and zymolysis is carried out so as to obtain a zymolysis product; the zymolysis product is fermented, ethanol is separated from the zymolysis product, and solid residue is recycled from a waste liquid, wherein, the skin of the raw potato materials is peeled by a potato shucking device; and the solid residue recycling method of the waste liquid comprises the steps of removing water from the waste liquid, obtaining a filter mass with water content that is less than 60 weight percent, drying the filter mass and obtaining the solid residue. The ethanol preparation method can improve ethanol yield and lower the energy consumption for recycling the solid residue from the waste liquid.
Description
Technical field
The invention relates to the preparation method of ethanol, more specifically about utilizing potato raw material to prepare the method for ethanol.
Background technology
The potato class, such as Ipomoea batatas, potato, cassava etc., therefore rich in starch is widely used in the fields such as fermentation sugaring, starch processed.
Cassava is that Perenniporia martius is perennial, the annual potato in temperate zone belongs to shrub, originates in South America, and suiting in medial temperature is 25-29 ℃, the growth of the low latitudes of average annual precipitation 1000-1500 millimeter.Before 1820, cassava is passed to southern china greatly, mainly in Guangdong, the plantation of Guangxi and Hainan, expand gradually now the provinces such as Yunnan, Fujian, Guizhou to.Cassava is divided into two classes: bitter manioc (poisonous cassava) and sweet taste cassava (nontoxic cassava).The main chemical compositions of fresh tapioca root is water, secondly is carbohydrate, also has less protein, fat and the pectin of some content.The fresh cassava starch content reaches the 25-30 % by weight.
Ripe the general thick 4-8 of cassava centimetre, long 20-30 centimetre, potato shape tubbiness, be the short cylindrical shape, cassava structure from inside to outside is followed successively by potato meat and epidermis, and epidermis comprises entocuticle and exterior skin, exterior skin is Vandyke brown, and an adularescent circular fringes, entocuticle and potato meat are white.
The epidermis of cassava particularly contains prussiate and a kind of cyanogen glucoside---phaseolunatin that can cause food poisoning in the entocuticle.Phaseolunatin is hydrolyzed rear generation prussic acid.Prussic acid and prussiate have severe toxicity, and it is very fast to poison.If the prussiate toxin is not removed yeast poison deactivation in the inactivation that can cause enzyme in the enzymolysis process and the fermenting process, thereby affects follow-up enzymolysis and fermenting process.Therefore, existing utilize potato raw material particularly the cassava method for preparing ethanol generally comprise first the potato raw material peeling, ethanol is isolated in and then pulverizing, enzymolysis and fermentation from tunning.
Present general artificial peeling or the simple machine barking of adopting rubs the epidermis of cassava or the epidermis of cassava reamed by rubbing effect.Because the epidermis of cassava particularly entocuticle is close on the potato meat, therefore, when removing the peel by rubbing effect, decortication effect is bad, also have quite a few epidermis to remain in the cassava surface, thereby make prussiate in the cassava residual large (the prussiate clearance is about 40-50%), cause yeast poison deactivation in the inactivation of enzyme in the enzymolysis process and the fermenting process, and then affect alcohol yied; Perhaps, when the epidermis of cassava is reamed, be easy to potato meat is got rid of, thereby lose a large amount of raw materials, also reduce inevitably alcohol yied.Existing utilize potato raw material particularly cassava to prepare the alcohol yied of method of ethanol lower.
In addition, owing to isolating the organism that the waste liquid that obtains after the ethanol contains high density from tunning, the waste liquid of present most ethanol factory discharging is through effectively processing directly outwards discharging, the water surrounding in local and downstream caused have a strong impact on.
At present, the treatment process of the waste liquid of preparation of ethanol by fermentation of cassava has: 1, burning method, be about to burn after waste liquid concentrates, and the shortcoming of the method easily causes secondary pollution after burning; 2, use the waste liquid ferment preparation of sludge gas, the shortcoming of the method is that investment is large and the control techniques requirement is high.
Therefore, the method that usually adopts the solid residue in the waste liquid that reclaims preparation of ethanol by fermentation of cassava to dispose waste liquid as feed at present, the method comprise anhydrates the waste liquid filtration, obtains filter cake; Afterwards filter cake is dried.The method is a kind of less investment, the easy treatment process of operation and the waste liquid of environment amenable preparation of ethanol by fermentation of cassava, but, adopt the energy consumption of the method larger, and the method is filtered the more serious wear to press apparatus of impurity in the water of removing, increased maintenance cost, and chemical oxygen demand value (COD value) is higher in the water of removing, and environmental stress is very large.
Summary of the invention
The objective of the invention is to overcome the lower and method that from waste liquid, reclaim solid residue of the existing alcohol yied that utilizes the method that potato raw material prepares ethanol and have the large shortcoming of energy consumption, provide a kind of can effectively improve alcohol yied and reduce the potato raw material that utilizes that from waste liquid, reclaims the energy consumption of solid residue prepare the method for ethanol.
The present inventor has carried out careful research to the existing method that reclaims solid residue from waste liquid, find in the existing method, the water content of the filter cake that obtains after waste liquid dewaters is usually up to more than 75 % by weight, and existing method also can't further reduce the water content of filter cake, thereby makes energy consumption required in the follow-up drying process higher.
The invention provides a kind of method of utilizing potato raw material to prepare ethanol, the method comprises to be pulverized potato raw material peeling with the potato raw material after the peeling, with the product after pulverizing mix with enzyme, enzymolysis, obtain enzymolysis product; This enzymolysis product ferments, separating alcohol from tunning, then from waste liquid, reclaim solid residue, wherein, the method of described potato raw material peeling is used a potato seed class peeling equipment, this potato class peeling equipment comprises support 1, cylinder 2, spiral feeder 3 and drive unit, cylinder 2 is installed in rotation on the support 1, cylinder 2 has opening for feed 4 and discharge port 5, described screwfeed device 3 is arranged in cylinder 2 and is fixedly connected with the inwall of cylinder, and described drive unit is used for head roll 2 and screwfeed device 3 rotates together; The method of this potato raw material peeling comprises to be put into potato raw material in the described cylinder 2 by described opening for feed 4, utilizes described drive unit head roll 2 and screwfeed device 3 to rotate together; The described method that reclaims solid residue from waste liquid comprises the water of removing in the waste liquid, obtains water content less than the filter cake of 60 % by weight, then filter cake is carried out drying, obtains solid residue.
According to barking method of the present invention the cassava raw material is removed the peel, the clearance of prussiate can reach more than 75%, and loss rate of raw materials can remain on below 5 % by weight, thereby is conducive to improve the productive rate of ethanol.Simultaneously, in the process that from waste liquid, reclaims solid residue, by reducing significantly the water content of the filter cake that obtains, thereby reduced significantly energy consumption required in the follow-up drying course.
Description of drawings
Fig. 1 is the front view of the used potato class peeling equipment of potato raw material barking method of the present invention;
Fig. 2 is the vertical profile schematic diagram of described potato class peeling equipment;
Fig. 3 is the cross-sectional schematic diagram of the annexation of expression sprocket wheel and cylinder.
Embodiment
The method of utilizing potato raw material to prepare ethanol provided by the invention, the method comprise to be pulverized potato raw material peeling with the potato raw material after the peeling, with the product after pulverizing mix with enzyme, enzymolysis, obtain enzymolysis product; This enzymolysis product that ferments, then separating alcohol from tunning reclaims solid residue from waste liquid, and wherein, the method for described potato raw material peeling is used a potato seed class peeling equipment.
As depicted in figs. 1 and 2, this peeling equipment comprises support 1, cylinder 2, spiral feeder 3 and drive unit (not shown), cylinder 2 rotationally, be mounted obliquely within on the support 1, cylinder 2 has opening for feed 4 and discharge port 5, described screwfeed device 3 is arranged in cylinder 2 and is fixedly connected with the inwall of cylinder, and described drive unit is used for head roll 2 and screwfeed device 3 rotates together.The method of potato raw material peeling is comprised that potato raw material puts in the described cylinder 2 by described opening for feed 4, utilize described drive unit head roll 2 and screwfeed device 3 to rotate together.The velocity of rotation of head roll 2 and screwfeed device 3 can be 2-50 rev/min, is preferably 5-25 rev/min.Under the pushing effect of screwfeed device 3, potato raw material constantly moves forward; Potato raw material is along with cylinder 2 and screwfeed device 3 rotate simultaneously, in rotation process, rub between the potato raw material, also rub between potato raw material and cylinder wall and the screwfeed device, thereby the epidermis of potato class is got rid of, and the potato class after the peeling is discharged from discharge port 5.
Described cylinder 2 can be made by various anti-abrasive materials, for example, and steel, rubber or rigid plastics.Can also be provided with spray equipment in the described cylinder 2, spray equipment can be fixedly mounted on the inwall of cylinder, and is positioned at the position near the opening for feed of cylinder.Described spray equipment can be the various spray equipments of routine.According to the present invention, the method can also be included in the peeling process water sprayed on the potato raw material by spray equipment the dirt on the potato raw material (such as earth, impurity etc.) is got rid of.Described injection flow rate is not particularly limited, as long as guarantee the dirt on the potato raw material is removed.
Under the preferable case, as shown in Figure 1, described cylinder 2 comprises first paragraph cylinder 2a and second segment cylinder 2b from the entrance end to the exit end, and first paragraph cylinder 2a and second segment cylinder 2b are communicated with, and are provided with spray equipment among the second segment cylinder 2b.Spray equipment can be fixedly mounted on the inwall of second segment cylinder 2b, and is positioned at the position near the opening for feed of second segment cylinder.
According to method of the present invention, in order to reach better decortication effect, also has friction structure on the inwall of described cylinder 2.Described friction structure can for various shaggy structures, be preferably one or more Ribbed Bar, more preferably the multi-ribbon rib reinforcement.Ribbed Bar has cross rib, can use hot rolled ribbed steel bar and the cold rolled reinforcing steel bar with ribs of conventional all size, as meets the Ribbed Bar of GB1499-1998 regulation.The nominal diameter of Ribbed Bar can be the 6-25 millimeter, is preferably the 8-20 millimeter; The cross rib spacing can be the 3-16 millimeter, is preferably the 4-12 millimeter.The trade mark of Ribbed Bar includes but not limited to HRB335, HRB400 and HRB500.Described Ribbed Bar is fixedly connected with the inwall of cylinder 2, and in the cylinder rotation process, Ribbed Bar can play rubbing effect to potato raw material.Be fixedly connected with Ribbed Bar for the ease of the inwall at cylinder 2, Ribbed Bar is preferably parallel with the central axis of cylinder 2.
Described cylinder 2 can flatly or be mounted obliquely within on the support 1.When described cylinder was flatly installed, potato raw material moved forward under the pushing effect of screwfeed device 3, finally discharged from the discharge port of cylinder.When described drum-inclined ground was installed, the position of opening for feed was higher than discharge port, and potato raw material can also move down by the action of gravity of self (namely moving forward).The angle of inclination of cylinder 2 can be the 0-15 degree, is preferably the 5-10 degree; The length of cylinder 2 can be 2-10 rice, is preferably 3.5-7 rice.When cylinder comprised described first paragraph cylinder and second segment cylinder, length herein referred to the length sum of first paragraph cylinder and second segment cylinder.Described angle of inclination refers to central shaft and the horizontal angle of cylinder.There is no particular limitation to the interior diameter of cylinder, can remove the peel as required the amount of the potato raw material of processing and select suitable cylinder interior diameter, and generally speaking, the cylinder interior diameter can be 1-2 rice.
Described screwfeed device 3 can be the various screwfeed devices of mechanical field routine.Described screwfeed device 3 can be fixedly connected with on the inwall that mode is connected to cylinder 2 by routine various, and for example, as shown in Figure 2, screwfeed device 3 is fixedly connected on the inwall of cylinder 2 by fastening piece 8.In order to reach better decortication effect, the pitch of described screwfeed device 3 is preferably 0.3-0.8 rice, and thread depth is preferably 0.1-0.4 rice.The screwfeed device can be made by various anti-abrasive materials, for example, and steel, rubber, nylon.
The present invention is not particularly limited described drive unit, as long as energy head roll 2 and screwfeed device 3 rotate together.For example, described drive unit can comprise drive source, transmission chain and sprocket 6.As shown in Figure 3, sprocket wheel 6 is fixed on the cylinder 2.When cylinder 2 comprises first paragraph cylinder 2a and second segment cylinder 2b, preferably sprocket wheel 6 is installed between first paragraph cylinder 2a and the second segment cylinder 2b.Because cylinder 2 is installed in rotation on the support 1, so transmission chain is with the transmission of power of drive source during to sprocket wheel, and sprocket wheel can drive cylinder and rotate.Rotating mounting means can be the whole bag of tricks of routine, for example, can use supporting roll or bracing frame that roller shelves is located on the support, and cylinder can be rotated around central shaft.Drive source can be for the various devices that can produce power, such as electric motor.
For the ease of charging, this peeling equipment can also comprise windmill feeder 7.Shown in Fig. 1 or 2, windmill feeder 7 is installed on the opening for feed 4 of cylinder.Windmill feeder 7 can be the various windmill feeders of mechanical field routine.
To adopt potato class peeling equipment of the present invention be between the potato raw material that utilizes in cylinder and the effect of the frictional force between potato raw material and the barrel and potato raw material is removed the peel.According to barking method of the present invention the cassava raw material is removed the peel, the clearance of prussiate can reach more than 75%, and loss rate of raw materials can remain on below 5 % by weight, thereby is conducive to improve the productive rate of ethanol.
Described potato raw material can be various potato raw materials, and such as Ipomoea batatas, potato, cassava etc., the potato raw material that adopts in the specific embodiments of the present invention is cassava.Owing to may contain earth, sandstone impurity and iron contamination in the potato raw material, can cause damage to peeling equipment, therefore, according to method of the present invention, before can also comprising peeling potato raw material is carried out pretreated routine operation, described pretreated step generally comprises the step of removing impurity and cleaning.As, after fresh cassava is gathered, remove earth, root, palpus and the impurity such as wooden part and sandstone on the cassava.And cassava cleaned, the method and apparatus of described cleaning is conventionally known to one of skill in the art.
According to the present invention, described breaking method can be the breaking method of this area routine, as long as the weave construction of cassava is destroyed, makes small starch granules can disintegrate from tapioca root, separate and get final product.For example, can adopt dry type to pulverize or case of wet attrition, the difference between two kinds of grinding modes mainly is whether cassava is mixed with water.Case of wet attrition comprises mixes the cassava after the peeling with water, then carry out one or many and pulverize.The average particulate diameter of the product after the pulverizing is preferably the 1.5-10 millimeter.The weight ratio of cassava and water can be 1: 0.2-1.2 is preferably 1: 0.8-1.Can use conventional various pulverizers, for example SFSP series beater disintegrating machine.
Described enzymolysis step can be finished by this area method commonly used, such as adding microbes producing cellulase and/or enzyme in crushed products, is incubated under the growth temperature of microbes producing cellulase and/or the great-hearted temperature of enzyme and finishes.Described microbes producing cellulase be can secreting amylase microbes producing cellulase.Described enzyme comprises amylase.
Because microorganism growth can produce by product, therefore preferably directly add enzyme.The consumption of described enzyme is The more the better, for cost consideration, the dry weight basis of the product after preferably pulverizing with every gram, described diastatic consumption is the 4-50 enzyme activity unit, the dry weight basis of the product after more preferably pulverizing with every gram, described diastatic consumption is the 10-30 enzyme activity unit.
The enzyme activity unit of enzyme of the present invention can in the pH value be 6.0, temperature is that 1 minute is converted into the required enzyme amount of glucose with 1 milligram of starch is an enzyme activity unit under 70 ℃ the condition.
The temperature of described enzymolysis can be diastatic any optimum temperature, is generally 50-90 ℃, more preferably 60-70 ℃.The longer the better on the time theory of described enzymolysis, considers plant factor, and the time of preferred described enzymolysis is 20-240 minute, more preferably 30-120 minute.The pH value of described enzymolysis can be generally 3.0-7.0 for diastatic the suitableeest any action pH, and more preferably the pH value is 5.0-6.0.Because the fluctuation of pH value is little in the enzymolysis process, therefore the pH value of described enzymolysis can be regulated before adding enzyme according to this area method commonly used, for example first crushed products and water or substratum (are enzyme-addedly generally mixed with water, add microbes producing cellulase generally with the substratum of this microorganism) mix, the solid content that generally makes the gained mixture is the 20-40 % by weight, pH value according to the gained mixture, the mixture pH regulator that to treat enzymolysis with sulphuric acid soln or sodium hydroxide more preferably is adjusted to the pH value and is 5.0-6.0 to 3.0-7.0.
Amylase is the general name of class of enzymes that can the starch-splitting glycosidic link, and described amylase generally comprises α-amylase, beta-amylase, saccharifying enzyme and isoamylase.Enzyme of the present invention comprises amylase.
α-amylase claims again starch Isosorbide-5-Nitrae-dextrinase, and it can cut the α-Isosorbide-5-Nitrae of starch chain inside-glycosidic link at random, brokenly, and Starch Hydrolysis is maltose, contains the oligosaccharides of 6 glucose units and with the oligosaccharides of side chain.The microorganism that produces this enzyme mainly has Bacillus subtilus, aspergillus niger, aspergillus oryzae and head mold.
Beta-amylase claims again starch Isosorbide-5-Nitrae-maltoside enzyme, can cut Isosorbide-5-Nitrae-glycosidic link from the starch molecule non reducing end, generates maltose.The product that this enzyme acts on starch is maltose and limit dextrin.This enzyme is mainly produced by aspergillus, head mold and endomyces.
Saccharifying enzyme claims again starch α-Isosorbide-5-Nitrae-glucuroide, and this enzyme acts on the non reducing end of starch molecule, take glucose as unit, acts on successively α-Isosorbide-5-Nitrae in the starch molecule-glycosidic link, generates glucose.This enzyme acts on that product behind the amylopectin has glucose and with α-1, the oligosaccharides of 6-glycosidic link; The product that acts on after the amylose starch almost all is glucose.It mainly is aspergillus niger (left U.S. aspergillus, Aspergillus awamori), head mold (snow-white enzyme, De Shi head mold), endomycopsi.sp, monascus that this enzyme produces bacterium.
Isoamylase claims again starch α-1, and 6-glucuroide, branching enzyme, this enzyme act on the α-1 at amylopectin molecule branching-point place, and the 6-glycosidic link downcuts the whole side chain of amylopectin and becomes amylose starch.It mainly is to dislike the bacteriums such as gas bacillus, genus bacillus and some Pseudomonas that this enzyme produces bacterium.
The enzyme that preferred described enzymolysis uses also comprises phosphoesterase.Because the phosphoric acid dextrin that phosphoesterase can make phosphoric acid and alcoholic hydroxyl be combined into ester is hydrolyzed into glucose, and discharge phosphoric acid, have the power that extremely significantly liquefies, so the enzyme that enzymolysis uses comprises phosphoesterase, hydrolyzed starch more fully is to increase alcohol yied.
The microorganism of monose such as glucose and/or fructose, oligosaccharides such as sucrose and/or semi-lactosi of can fermenting may be used to fermenting process of the present invention, because yeast saccharomyces cerevisiae is the microorganism of the zymohexose that ethanol-tolerant, by product are few, alcohol yied is high generally used on the wine industry, therefore the employed yeast of preferred described fermentation is yeast saccharomyces cerevisiae.
In every gram enzymolysis product, the inoculum size of the employed yeast of described fermentation is 10
3-10
8Colony-forming unit, more preferably 10
4-10
6Colony-forming unit.
Described colony-forming unit is defined as the method for a certain amount of bacterium liquid after the dilution by cast or coating, allows unicellular being dispersed in one by one on the culture medium flat plate of microorganism in it, and after cultivating, each viable cell just forms a bacterium colony.It is the single celled number that contains in every milliliter of bacterium liquid.
Employed yeast is fermented in the present invention can be for being purchased yeast solids preparation (such as dried yeast powder) or barms, such as No. 2 (Rasse II) yeast in Lars, have another name called No. two yeast of Germany, No. 12 (Rasse XII) yeast in Lars, have another name called Germany No. 12 yeast, K word yeast, No. five yeast in Nanyang (1300) and Nanyang mixed yeasts (1308).The colony-forming unit of described yeast can be measured by means commonly known in the art, such as the methylene blue staining viable bacteria counting method.The concrete grammar of methylene blue staining viable bacteria counting method is as follows:
1 gram dried yeast powder is dissolved in 10 ml sterile waters, or 1 milliliter of actication of culture liquid is diluted to 10 milliliters with sterilized water, add 0.5 milliliter of 0.1 % by weight methylene blue, 35 ℃ of lower insulations 30 minutes.Under 10 times of opticmicroscopes, with the number (dead bacterium dyeing, viable bacteria is not dyeed) of viable bacteria in the solution after the blood counting chamber counting insulation, can get the number of viable bacteria in 1 gram dry yeast or the 1 milliliter of actication of culture liquid, i.e. colony forming single-digit.
Described yeast can adopt conventional method inoculation, for example adds the seed liquor of 5-15 volume % in the enzymolysis product.Described seed liquor can be the aqueous solution or the culture medium solution of dry yeast, also can or be purchased the activated seed liquid of bacterial classification for dry yeast.
The temperature of described fermentation can be any temperature that is suitable for yeast growth, is preferably 30-36 ℃, more preferably 30-33 ℃.The pH value is 4-6, is preferably 4-4.5.The time of described fermentation can be for beginning from inoculation to occur to the decline phase of yeast growth the time of (being that fermentation time is that lag phase, logarithmic phase add stationary phase), and the time of preferred fermentation is 55-70 hour, more preferably 60-70 hour.Tunning ethanol can be with conventional method, according to requirement (requiring the purity of ethanol to reach more than 99% such as the fuel alcohol) separation and refining of different Industrial products, such as distilling, concentrate, dewatering.
From tunning, isolate after the ethanol, from waste liquid, reclaim waste residue.The described method that reclaims solid residue from waste liquid comprises the water of removing in the waste liquid, obtains water content less than the filter cake of 60 % by weight, then filter cake is carried out drying, obtains solid residue.
According to the present invention, described water content can obtain by variety of way less than the filter cake of 60 % by weight, for example can obtain by described waste liquid filtered and squeeze.
The present inventor has carried out careful research to the existing method that reclaims solid residue from the waste liquid of preparation of ethanol by fermentation of cassava, find usually to use in the prior art common pressure filter that the waste liquid of preparation of ethanol by fermentation of cassava is filtered, waste liquid enters between the common filter plate of pressure filter when filtering, solid particulate is trapped in the space between the filter plate by the filtration medium of filter plate, liquid then passes through filtration medium, discharge outside the pressure filter by portalling, continuity along with filtration procedure, the thickness of filter cake increases gradually, the resistance of dehydration increases exponentially thereupon, thereby cause the rapid decline for the treatment of capacity, and because the restriction of common filter plate nature, filter pressure can't further improve (generally below 1MPa), thereby can't further reduce the water content that obtains filter cake.
According to the present invention, can use various device that described waste liquid is filtered and squeezes, under the preferable case, can realize with diaphragm filter press, diaphragm filter press has the filtering function identical with the common diaphragm pressure filter, have again filter cake is squeezed and function that it is dewatered again, in diaphragm filter press, common filter plate and membrane filter plate are spaced, the middle central layer of described membrane filter plate and both sides barrier film compress and form two Sealed sandwiches, the filtering function of described membrane filter plate is identical with common filter plate, but has increased pressing function, namely, after filtering end, extrusion medium is injected into the Sealed sandwich from middle central layer hand-hole, because the elastic contribution of barrier film can carry out to the filter cake after filtering the blow-up squeezing, and filter cake is dewatered again.
The quantity of common filter plate and membrane filter plate can be adjusted according to the concentration of waste liquid in the described diaphragm filter press, under the preferable case, the quantity of common filter plate is 50-60, and described common filter plate can be commercially available, for example the chamber filter plate of Jingjin Filter Press Group Co.,Ltd's production; The quantity of membrane filter plate is 50-60, and described membrane filter plate can be commercially available, for example 1250 type membrane filter plates of Jingjin Filter Press Group Co.,Ltd's production; Common filter plate is spaced with membrane filter plate and the ratio of the quantity of common filter plate and the quantity of membrane filter plate is 1: 1; The diaphragm filter press that meets above-mentioned requirements can be commercially available, for example, and the X that Jingjin Filter Press Group Co.,Ltd produces
M AZG600/1500 * 2000U
B KThe diaphragm filter press of model.
The inventor finds, uses diaphragm filter press not only can reduce significantly the water content of squeezing the filter cake that obtains, and can also significantly reduce the content that squeezes impurity in the water of removing, and has reduced the wearing and tearing of impurity to equipment, has reduced maintenance cost; And the COD value is also lower in the water of removing, and has alleviated environmental stress.
Among the present invention, the condition of described filtration has no particular limits, and under the preferable case, the condition of described filtration comprises that the pressure of filtration is 0.4-1MPa, and the time of filtration is 2-8 hour; More preferably, the condition of described filtration comprises that the pressure of filtration is 0.5-0.8MPa, and filtration time is 4-6 hour.
According to the present invention, the condition of described squeezing has no particular limits, and under the preferable case, the condition of described squeezing comprises that the pressure of squeezing is 10-25MPa, and the time of squeezing is 0.2-2 hour; More preferably, the condition of described squeezing comprises that the pressure of squeezing is 15-20MPa, and the time of squeezing is 0.5-1 hour.
Among the present invention, described squeeze pressure can realize by be filled with extrusion medium in diaphragm filter press, and described extrusion medium can be diaphragm filter press various extrusion medium commonly used, and for example, described extrusion medium can be pressurized air and/or water.
According to the present invention, described drying means is preferably oven dry.The equipment of described oven dry can be the drying plant of various routines, for example, and WJI-900B boiling drier and the combined dryer of XLS-100 type flash dryer that the HZG series dryer that the long-range company in Shenyang produces and Beijing benefit civilian worker trade company limited produce.Among the present invention, the condition of described oven dry is conventionally known to one of skill in the art, and for example, the condition of described oven dry comprises that bake out temperature is 100-200 ℃, and drying time is 0.2-2 hour; More preferably, bake out temperature is 120-150 ℃, and drying time is 0.5-1 hour.
The present invention will be described in more detail below by embodiment.
Used cassava raw material is the new fresh cassava with a collection of results among the embodiment, and thick 4-8 centimetre, long 20-30 centimetre, water content is about 65 % by weight.
Embodiment 1
The present embodiment is used for illustrating that employing cassava raw material of the present invention prepares the method for ethanol.
(1) peeling of cassava raw material and pulverizing
Be prepared as follows the peeling equipment shown in Fig. 1,2 and 3.
Cylinder 2 comprises first paragraph cylinder 2a and second segment cylinder 2b from top to bottom, and first paragraph cylinder 2a and second segment cylinder 2b are communicated with, and the length of first paragraph cylinder 2a and second segment cylinder 2b is respectively 1.8 meters and 1.6 meters; Described cylinder 2 is formed from steel, and interior diameter is 1.6 meters; (trade mark is HRB335 to fix the hot rolled ribbed steel bar that 40 length are 1.5 meters on the inwall of first paragraph cylinder 2a, nominal diameter is 12 millimeters), each bar hot rolled ribbed steel bar is parallel with the central axis of cylinder, each bar hot rolled ribbed steel bar distributes equally spacedly along the circumference of inner wall of rotary drum, and the circumferential distance between adjacent two hot rolled ribbed steel bars is 0.125 meter; (trade mark is HRB500 to fix the hot rolled ribbed steel bar that 50 length are 1.2 meters on the inwall of second segment cylinder 2b, nominal diameter is 16 millimeters), each bar hot rolled ribbed steel bar is parallel with the central axis of cylinder, each bar hot rolled ribbed steel bar distributes equally spacedly along the circumference of inner wall of rotary drum, and the circumferential distance between adjacent two hot rolled ribbed steel bars is 0.1 meter; Cylinder 2 is mounted obliquely within on the support 1, and the angle of inclination is 5 degree.Screwfeed device 3 is made by rubber, and pitch is 0.5 meter, and thread depth is 0.2 meter; Screwfeed device 3 is fixedly connected on the inwall of cylinder 2 by fastening piece 8.Drive unit comprises electric motor, transmission chain and sprocket 6; Sprocket wheel 6 is fixed on the cylinder 2, and to sprocket wheel, the power of electric motor is 5.5 kilowatts to transmission chain with the transmission of power of electric motor.
Actuating motor makes cylinder 2 and screwfeed device 3 rotate (rotating speed is 7 rev/mins) around the central shaft of cylinder; The new fresh cassava of double centner surface clean of results is joined in the cylinder 2 by opening for feed 4 continuously, and the cassava after the peeling is discharged from discharge port 5, collects and obtains 96 kilograms of cassava raw materials after the peeling.
To be cut into 1 centimetre of disk that the left and right sides is thick after these 96 kilograms of cassava raw materials cleanings, then with SFSP series beater disintegrating machine the cassava slice after removing the peel is pulverized, the method of described pulverizing comprises that the cassava after will removing the peel first pulverizes, and obtaining average particulate diameter is 96 kilograms of crushed products of 6 millimeters (using the AccuSizerTM 780 optics particle diameter detectors of U.S. PPS company to record).
Get the above-mentioned crushed products of 20 grams, utilize the standard detecting method EPA335.3 of American National Environmental Protection Agency detection cyanide content wherein, note is C1.
Fresh Cassava crushing (average particulate diameter is 0.8mm) form slurry with the surface clean before the peeling, from the slurry that obtains, get 20 grams, add 180 gram distilled water, make sample to be detected, utilize the standard detecting method EPA335.3 of American National Environmental Protection Agency detection cyanide content wherein, note is C2.
Calculate the clearance of the rear prussiate of peeling by following formula:
ε
2＝(C2-0.96C1)/C2×100％
The prussiate clearance that calculates is 76%.
(2) enzymolysis
The crushed products of step (1) is mixed with 35 kg water, regulate pH value to 5, be heated to 80 ℃ after, with the dry weight basis of every gram crushed products, the α-amylase (Novozymes Company buys) that adds 20 enzyme activity units, and the insulation enzymolysis obtained enzymolysis product after 60 minutes under 80 ℃.
(3) fermentation and separating alcohol
Make the temperature of enzymolysis product be down to 33 ℃, with the weighing scale of every gram enzymolysis product, inoculation 10
5The distillery yeast of colony-forming unit (the super highly active dry yeast in Angel, Hubei Angel Yeast stock company), the gained mixture under 33 ℃ in fermentor tank stir culture 65 hours, at 100 ℃ of distillation gained tunnings, the gained distillation fraction can get 13.9 kilograms of ethanol at 78.3 ℃ of lower second distillations.Be calculated according to the following formula alcohol yied:
The fresh weight of alcohol yied=100% * ethanol weight/cassava raw material
Calculating alcohol yied is 13.9%.
(4) waste liquid with the potato raw material alcohol prepared by fermenting in the fermentor tank takes out from fermentor tank, and water flushing fermentor tank mixes the waste liquid of taking-up and the water after the flushing.
The waste liquid of 15 batches of above-mentioned fermentations is mixed, and (Shanghai Precision Scientific Apparatus Co., Ltd, the water content that SH-10A) detects in this mixed waste liquor is 85 % by weight by moisture determination instrument.Get 1 ton of this mixed waste liquor and join diaphragm filter press (Jingjin Filter Press Group Co.,Ltd, X
M AZG600/1500 * 2000U
B K) in filter, the quantity of common filter plate in the described diaphragm filter press (Jingjin Filter Press Group Co.,Ltd, chamber filter plate) is 50, membrane filter plate (Jingjin Filter Press Group Co.,Ltd, 1250 types) quantity is 50, and common filter plate and membrane filter plate are spaced; The condition of described filtration comprises that the pressure of filtration is 0.8MPa, and the time of filtration is 2 hours, obtains filter cake; Be filled with afterwards the extrusion medium air in membrane filter plate, the filter cake after filtering is squeezed, the pressure of described squeezing is 10MPa, and the time of squeezing is 2 hours, the filter cake A1 that obtains.
(result is as shown in table 1 for Shanghai Precision Scientific Apparatus Co., Ltd, the SH-10A) water content of detection filter cake A1 by moisture determination instrument.
The filter cake A1 that obtains is put into (Zhengzhou Wangu Machinery Co., Ltd. in the air-flow tumble-type dryers, JB/T10279-2001) dry, the temperature of oven dry is 120 ℃, the time of oven dry is 1.5 hours, obtain solid residue D1, (water content of solid residue D1 and the energy consumption of oven dry are as shown in table 1 for Shanghai Precision Scientific Apparatus Co., Ltd, the SH-10A) water content of detection solid residue D1 by moisture determination instrument.
Described energy consumption refers to dry the weight of the coal that the water of removing 1 kilogram consumes, and unit is kg/kg.
Comparative Examples 1
This Comparative Examples is used for illustrating that existing employing cassava raw material prepares the method for ethanol.
Method according to embodiment 1 prepares ethanol, makes 12.6 kilograms of ethanol, and different is that the method for the artificial peeling of employing scrapes off with the entocuticle of cutter with the cassava raw material in step (1), collects and obtains 96 kilograms of cassava raw materials after the peeling.Calculating alcohol yied according to the method identical with embodiment 1 is 12.6%.Measure cyanide content before and after the peeling according to the method identical with embodiment 1, and to calculate the prussiate clearance be 62%.
In addition, in step (4), with membrane filter plate (Jingjin Filter Press Group Co.,Ltd, 1250 types) replace with common filter plate (Jingjin Filter Press Group Co.,Ltd, chamber filter plate), the condition of described filtration comprises that the pressure of filtration is 0.8MPa, and the time of filtration is 2 hours, obtains reference filter cake CA1.
(result is as shown in table 1 for Shanghai Precision Scientific Apparatus Co., Ltd, the SH-10A) water content of detection reference filter cake CA1 by moisture determination instrument.
The reference filter cake CA1 that obtains is put into (Zhengzhou Wangu Machinery Co., Ltd. in the air-flow tumble-type dryers, JB/T10279-2001) dry, the temperature of oven dry is 120 ℃, the time of oven dry is 1.5 hours, obtain solid residue CD1, (water content of reference solid residue CD1 and the energy consumption of oven dry are as shown in table 1 for Shanghai Precision Scientific Apparatus Co., Ltd, the SH-10A) water content of detection reference solid residue CD1 by moisture determination instrument.
Described energy consumption refers to dry the coal that the water of removing 1 kilogram consumes, and unit is kg/kg.
Can find out from the result of above-described embodiment 1 and Comparative Examples 1, alcohol yied is 13.9% among the embodiment 1, and alcohol yied is 12.6% in the Comparative Examples 1, compares with Comparative Examples 1, and the alcohol yied among the embodiment 1 has improved 10.3%; From the prussiate clearance, the prussiate clearance of embodiment 1 is 76%, and the prussiate clearance of Comparative Examples 1 is 62% only, and the productive rate that adopts method of the present invention can greatly improve ethanol is described.
The present embodiment is used for illustrating that employing cassava raw material of the present invention prepares the method for ethanol.
Method according to embodiment 1 prepares ethanol, and different is, in step (4): waste liquid is joined diaphragm filter press (Jingjin Filter Press Group Co.,Ltd, X
M AZG600/1500 * 2000U
B K) in filter, the quantity of common filter plate in the described diaphragm filter press (Jingjin Filter Press Group Co.,Ltd, chamber filter plate) is 60, membrane filter plate (Jingjin Filter Press Group Co.,Ltd, 1250 types) quantity is 60, and common filter plate and membrane filter plate are spaced; The condition of described filtration comprises that the pressure of filtration is 0.4MPa, and the time of filtration is 8 hours, obtains filter cake; Be filled with afterwards the extrusion medium air in membrane filter plate, the filter cake after filtering is squeezed, the pressure of described squeezing is 25MPa, and the time of squeezing is 0.2 hour, the filter cake A2 that obtains.
(result is as shown in table 1 for Shanghai Precision Scientific Apparatus Co., Ltd, the SH-10A) water content of detection filter cake A2 by moisture determination instrument.
The filter cake A2 that obtains is put into (Zhengzhou Wangu Machinery Co., Ltd. in the air-flow tumble-type dryers, JB/T10279-2001) dry, the temperature of oven dry is 180 ℃, the time of oven dry is 0.5 hour, obtain solid residue D2, (water content of solid residue D2 and the energy consumption of oven dry are as shown in table 1 for Shanghai Precision Scientific Apparatus Co., Ltd, the SH-10A) water content of detection solid residue D2 by moisture determination instrument.
The present embodiment is used for illustrating that employing cassava raw material of the present invention prepares the method for ethanol.
Method according to embodiment 1 prepares ethanol, and different is, in step (4): waste liquid is joined diaphragm filter press (Jingjin Filter Press Group Co.,Ltd, X
M AZG600/1500 * 2000U
B K) in filter, the quantity of common filter plate in the described diaphragm filter press (Jingjin Filter Press Group Co.,Ltd, chamber filter plate) is 55, membrane filter plate (Jingjin Filter Press Group Co.,Ltd, 1250 types) quantity is 55, and common filter plate and membrane filter plate are spaced; The condition of described filtration comprises that the pressure of filtration is 0.5MPa, and the time of filtration is 6 hours, obtains filter cake; Be filled with afterwards the extrusion medium air in membrane filter plate, the filter cake after filtering is squeezed, the pressure of described squeezing is 20MPa, and the time of squeezing is 0.5 hour, the filter cake A3 that obtains.
(result is as shown in table 1 for Shanghai Precision Scientific Apparatus Co., Ltd, the SH-10A) water content of detection filter cake A3 by moisture determination instrument.
The filter cake A3 that obtains is put into (Zhengzhou Wangu Machinery Co., Ltd. in the air-flow tumble-type dryers, JB/T10279-2001) dry, the temperature of oven dry is 120 ℃, the time of oven dry is 0.5 hour, obtain solid residue D3, (water content of solid residue D3 and the energy consumption of oven dry are as shown in table 1 for Shanghai Precision Scientific Apparatus Co., Ltd, the SH-10A) water content of detection solid residue D3 by moisture determination instrument.
Table 1
| The embodiment numbering | Cake moisture (% by weight) | Solid residue water content (% by weight) | Energy consumption (kg/kg) |
| Embodiment 1 | 60 | 10％ | 0.17 |
| Comparative Examples 1 | 78 | 10％ | 0.31 |
| |
50 | 11％ | 0.09 |
| |
55 | 12％ | 0.12 |
Can find out from the result shown in the table 1, the water content of the filter cake A1-A3 that embodiment of the invention 1-3 obtains is respectively 60 % by weight, 50 % by weight and 55 % by weight, energy consumption is respectively 0.17,0.09 and 0.12, the water content of the reference filter cake CA1 that Comparative Examples 1 obtains is then up to 78 % by weight, energy consumption is also up to 0.31, illustrate that method of the present invention is reclaiming in the process of solid residue from waste liquid, by reducing significantly the water content of the filter cake obtain, thereby reduced significantly energy consumption required in the follow-up drying course.
Claims (17)
1. method of utilizing potato raw material to prepare ethanol, the method comprise the potato raw material peeling, the potato raw material after the peeling is pulverized, with the product after pulverizing mix with enzyme, enzymolysis, obtain enzymolysis product; This enzymolysis product ferments, separating alcohol from tunning, then from waste liquid, reclaim solid residue, it is characterized in that, the method of described potato raw material peeling is used a potato seed class peeling equipment, this potato class peeling equipment comprises support (1), cylinder (2), spiral feeder (3) and drive unit, cylinder (2) is installed in rotation on the support (1), cylinder (2) has opening for feed (4) and discharge port (5), described screwfeed device (3) is arranged in cylinder (2) and is fixedly connected with the inwall of cylinder, and described drive unit is used for head roll (2) and screwfeed device (3) rotates together; The method of this potato raw material peeling comprises to be put into potato raw material in the described cylinder (2) by described opening for feed (4), utilize described drive unit head roll (2) and screwfeed device (3) to rotate together, have friction structure on the inwall of described cylinder (2); The described method that reclaims solid residue from waste liquid comprises the water of removing in the waste liquid, obtains water content less than the filter cake of 60 % by weight, then filter cake is carried out drying, obtains solid residue.
2. method according to claim 1, wherein, described friction structure is one or more Ribbed Bar.
3. method according to claim 2, wherein, described Ribbed Bar is parallel with the central axis of cylinder (2).
4. method according to claim 1, wherein, the angle of inclination of described cylinder (2) is the 0-15 degree, length is 2-10 rice; The velocity of rotation of cylinder (2) and screwfeed device (3) is 2-50 rev/min.
5. according to claim 1 or 4 described methods, wherein, the pitch of described screwfeed device (3) is 0.3-0.8 rice, and thread depth is 0.1-0.4 rice.
6. method according to claim 1, wherein, described drive unit comprises drive source, transmission chain and sprocket (6), sprocket wheel (6) is fixed on the cylinder (2), transmission chain with the transmission of power of drive source to sprocket wheel.
7. method according to claim 1, wherein, the average particulate diameter of the product after the pulverizing is the 1.5-10 millimeter.
8. method according to claim 1, wherein, the enzyme that described enzymolysis uses comprises amylase, with the dry weight basis of every gram potato raw material, described diastatic consumption is the 4-50 enzyme activity unit; The temperature of described enzymolysis is 50-90 ℃, and the time of described enzymolysis is 20-240 minute, and the pH value of described enzymolysis is 5-6.
9. method according to claim 8, wherein, described amylase is one or more in α-amylase, saccharifying enzyme, beta-amylase and the isoamylase.
10. method according to claim 1, wherein, in every gram enzymolysis product, the inoculum size of the employed yeast of described fermentation is 10
3-10
8Colony-forming unit, the temperature of described fermentation are 30-33 ℃, and the time of fermentation is 50-75 hour.
11. method according to claim 1, wherein, described water content obtains by described waste liquid is filtered and squeezes less than the filter cake of 60 % by weight.
12. method according to claim 11, wherein, the condition of described filtration comprises that the pressure of filtration is 0.4-1MPa, and the time of filtration is 2-8 hour.
13. method according to claim 12, wherein, the condition of described filtration comprises that the pressure of filtration is 0.5-0.8MPa, and filtration time is 4-6 hour.
14. method according to claim 11, wherein, the condition of described squeezing comprises that the pressure of squeezing is 10-25MPa, and the time of squeezing is 0.2-2 hour.
15. method according to claim 14, wherein, the condition of described squeezing comprises that the pressure of squeezing is 15-20MPa, and the time of squeezing is 0.5-1 hour.
16. method according to claim 1, wherein, the condition of described drying comprises that drying temperature is 100-200 ℃, and be 0.2-2 hour time of drying.
17. method according to claim 11, wherein, described filtration and squeezing realize by diaphragm filter press.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100562145A CN101487024B (en) | 2008-01-15 | 2008-01-15 | Method for preparing ethanol from tuber crops raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100562145A CN101487024B (en) | 2008-01-15 | 2008-01-15 | Method for preparing ethanol from tuber crops raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101487024A CN101487024A (en) | 2009-07-22 |
| CN101487024B true CN101487024B (en) | 2013-03-06 |
Family
ID=40890085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100562145A Active CN101487024B (en) | 2008-01-15 | 2008-01-15 | Method for preparing ethanol from tuber crops raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101487024B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102168009A (en) * | 2010-02-25 | 2011-08-31 | 中粮集团有限公司 | System for preparing ethanol by adopting potato type raw materials |
| CN105463032B (en) * | 2015-12-14 | 2019-01-18 | 山西大同大学 | A kind of preprocess method of fuel ethyl hydrate raw material cassava |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1644703A (en) * | 2004-12-29 | 2005-07-27 | 天津大学 | Production of alcohol fuel |
| CN101041849A (en) * | 2007-04-26 | 2007-09-26 | 湖南南方马铃薯产业化工程技术有限公司 | Method for producing fuel ethanol by using potato as raw material |
-
2008
- 2008-01-15 CN CN2008100562145A patent/CN101487024B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1644703A (en) * | 2004-12-29 | 2005-07-27 | 天津大学 | Production of alcohol fuel |
| CN101041849A (en) * | 2007-04-26 | 2007-09-26 | 湖南南方马铃薯产业化工程技术有限公司 | Method for producing fuel ethanol by using potato as raw material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101487024A (en) | 2009-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hargreaves et al. | Production of ethanol 3G from Kappaphycus alvarezii: evaluation of different process strategies | |
| CN101186943B (en) | Method for producing ethanol from crop straw | |
| CN100489108C (en) | Process for producing ethanol by using potatoes as raw material | |
| CN101487025B (en) | Method for preparing ethanol from tuber crops raw material | |
| CN106834358A (en) | A kind of method that Efficient Conversion algal polysaccharides prepare bio-ethanol | |
| CN101487027B (en) | Method for preparing ethanol from tuber crops raw material | |
| CN101487024B (en) | Method for preparing ethanol from tuber crops raw material | |
| CN111363765B (en) | Method for preparing lactic acid by fermentation | |
| CN101676393B (en) | Method for preparing alcohol by utilizing potato materials | |
| CN101289675B (en) | Process for producing ethanol by using potatoes as raw material | |
| CN101676397B (en) | Method for preparing alcohol by utilizing potato materials | |
| CN102876731B (en) | Method for producing biological butanol by rice hull | |
| CN101676398B (en) | Method for preparing alcohol by utilizing potato materials | |
| CN101676395B (en) | Method for preparing alcohol by utilizing potato materials | |
| CN101676396B (en) | Method for preparing alcohol by utilizing potato materials | |
| CN101487026B (en) | Method for preparing ethanol from tuber crops raw material | |
| CN101586123B (en) | Method for preparing ethanol by adopting yam materials | |
| CN101988077A (en) | Method for preparing ethanol from potato raw material | |
| CA3145113A1 (en) | A strain of trichoderma reesei and culture method and use thereof | |
| CN101586125B (en) | Method for preparing ethanol from yam raw materials | |
| CN101676394B (en) | Method for preparing alcohol by utilizing potato materials | |
| CN104232694A (en) | Preparation process of energy conservation and environmental protection alcohol | |
| CN102168112B (en) | Method for preparing ethanol by using tuber raw materials | |
| CN101586124B (en) | Method for preparing ethanol by adopting yam materials | |
| CN102909109B (en) | Methods for degerming and pretreating corns and method for brewing alcohol by adopting corns |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |