CN102619118B - Hydrolytic treatment method for straw hemicellulose - Google Patents
Hydrolytic treatment method for straw hemicellulose Download PDFInfo
- Publication number
- CN102619118B CN102619118B CN201210005719.5A CN201210005719A CN102619118B CN 102619118 B CN102619118 B CN 102619118B CN 201210005719 A CN201210005719 A CN 201210005719A CN 102619118 B CN102619118 B CN 102619118B
- Authority
- CN
- China
- Prior art keywords
- pickling
- acid
- raw material
- hydrolysis
- stalk
- 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
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Preparation Of Fruits And Vegetables (AREA)
Abstract
The invention discloses a hydrolytic treatment method for straw hemicellulose. The hydrolytic treatment method includes steps: a, compressing and squeezing raw materials to form blocks, and filling the raw material blocks into a hydrolysis tank; b, quickly pickling the raw material blocks in the hydrolysis tank until the raw material blocks are thoroughly pickled; and c, removing free acid and feeding steam into the hydrolysis tank to hydrolyze the pickled raw material blocks. By the aid of the method, high workload for crushing straw in a traditional method is omitted, and large quantities of labor and materials are saved. In addition, the raw material blocks are pickled and hydrolyzed in the hydrolysis tank, a pickling tank is omitted as compared with a traditional mode that raw materials need to be pickled in the pickling tank at first and then are fished out to be filled in a hydrolysis tank to be hydrolyzed, and huge quantities of labor and equipment are saved.
Description
Technical field
The present invention relates to the hydrolysis process for treating of stalk hemicellulose.
Background technology
Stalk is the general name of remaining stem after ripe gramineae crop has gathered in the crops seed, leaf, fringe part, also the bagasse squeezed after sugar is comprised, its main component comprises lignin, cellulose and hemicellulose three parts, these three kinds of compositions are cellulose 30-50% in the general ratio of Different Crop stalk, hemicellulose 20-35%, lignin 20-30%.Wherein cellulosic hydrolysates is glucose (hexose), and hydrolysis of hemicellulose product is mainly wood sugar, arabinose (being pentose), and lignin degradation thing is the compound containing phenyl ring of series of complex.
Stalk hemicellulose part is easy to by dilute acid hydrolysis, the hemicellulose hydrolysate that to generate with pentose (wood sugar, arabinose) be main component.Functional sweetener crystalline xylose can be directly prepared after hemicellulose dilute acid hydrolysis thing is purified, arabinose, or directly the wood sugar in hydrolysate is reduced to the higher functional sweetener xylitol of added value by biofermentation, or xylose-fermenting produces all kinds of chemical products comprising alcohol fuel.In addition, the wood sugar in hemicellulose hydrolysate also through dehydration, can generate important industrial chemicals furfural.Although stalk resource is very abundant, hemicellulose wherein, also very easily by dilute acid hydrolysis, obtain cheap hemicellulose hydrolysate not a duck soup.Because stalk is bulky, volume density is low, and traditional method for hydrolysis not only steam, acid solution consumption is large, and hydrolysis device utilization ratio is also very low.Meanwhile, the final entered environment of acid solution that hydrolytic process consumes, acid solution consumption is larger, and the environmental improvement burden of stalk hydrolysis factory is heavier.Therefore, according to existing half fiber hydrolysis process, no matter be furfurol industry, or wood sugar (alcohol) industry, all produce the waste water, the waste residue that are difficult in a large number administer, belong to typical high energy consumption, heavy polluted industry.
Prepare the technique of wood sugar for traditional dilute acid hydrolysis method hydrolysis of corncob, Bagasse Hemicellulose, raw material adds sulfuric acid solution and makes terminal sulfuric acid concentration reach 1-1.5%, passing into steam, 115--130 DEG C of Water Under solution 1.5-2h after loading hydrolysis kettle.The hydrolyzate sugar content that hydrolysis terminates namely to leach is different because of raw material, between about 2.5-6%.For improving the rate of recovery of wood sugar, in tank, residue must boil once with clear water usually again, the sugary about 1-2% of water cooking liquid, is hydrolyzed after supplying acid for next group material.Not only hydrolytic process power consumption is large for the liquid hydrolysis process of this stalk hemicellulose, and gained hydrolyzate sugar concentration is also very low.For corncob, the total sugar concentration of liquid hydrolyzate is generally no more than 6%, and the total sugar concentration of the liquid hydrolyzate of bagasse is even difficult to more than 3%.Too low sugared concentration adds follow-up concentrated burden.
In fact, only have the acid of immersing stalk organization internal to be only the effective acid participating in catalytic hydrolysis reaction, the free acid solution in material gap belongs to the invalid acid not participating in reacting.With corncob, this kind of stalk being widely used in hydrolysis of bagasse is example, the voidage of their natural packings is generally more than 50%, the free acid solution being in gap not only wastes heat energy, also the sugared concentration of hydrolyzate is diluted, increase the concentrated expense in later stage, increase the weight of the burden of hydrolyzate purification and environmental improvement simultaneously.
If stalk tissue soaks into acid solution, be hydrolyzed same temperature conditions as long as obtain with liquid state, the acid hydrolytic reaction of stalk obviously can carry out equally.Steam obtains to be hydrolyzed the effective medium of same temperature conditions with liquid state, soaks into the stalk of acid solution in steam state Water Under solution, the many defects obviously liquid just can being avoided to be hydrolyzed, and significantly reduces stalk hydrolysis production cost.But stalk is organized dense, institutional framework without destroy stalk and be not easy to soak into acid solution very soon.Such as, intact corn core needs time a couple of days just can soak into acid solution usually.The people such as Luo Peng steep for 0.5% dilute sulfuric acid and cut off wheat straw raw material, and the processing time still needs 12 hours.(Luo Peng Liu Zhong king promotion, acid catalyzed steam blasting pre-processing intensity is to the research of wheat straw Enzymatic Hydrolysis.Chemistry of forest product and industry; 2006,26(4): 105-109).The long pickling processing time will have a strong impact on stalk hydrolysis production efficiency, become infeasible in actual production.
Stalk is pulverized, then is sprayed onto on comminuting matter by acid solution, because contact surface expands, acid solution diffusion length shortens, and also can play the effect accelerating pickling.Such as, the sulfuric acid of 15% is sprayed to the surface of crushing maize core by the people such as Zhao Hui, infiltrates certain hour, then is hydrolyzed by Steam Heating, the hemicellulose hydrolysate reducing sugar degree of depth extracted can reach 13%(Zhao Hui Wu state peak Zhang Kechang, the research of corncob hemicellulose normal pressure acid hydrolysis technology.Heilongjiang University's natural science journal, 2003,20(1), 118-12).But necessary drying process before being pulverized by stalk, crushing process also needs consumption of power, and spray acid, the process of pulverizing also needs to take a large amount of place and equipment.This obviously improves the production cost of stalk hydrolysis.
If the stalk without pulverizing can be utilized to carry out steam state acid hydrolysis, the tedious procedure that raw material is pulverized just can be removed from.But must can realize rapid pickling, utilizing the stalk without pulverizing to carry out the acid-hydrolyzed technique of steam state just has actual application value.If the dress pot density of stalk at hydrolytic decomposition pot can be improved on this basis further, this steam state benefit that hydrolysis process plays, be conventional liquid hydrolysis process incomparable.
Summary of the invention
An object of the present invention, be to provide a kind of steam state to be hydrolyzed the method for the stalk of the broken process of untreated powder, too low with sugared concentration after the hydrolysis solving background technology, invalid acid solution is too much, waste heat energy and later stage concentrate the problems such as expense, and this cumbersome process of pulverizing that economizes in raw materials.
Another object of the present invention, is to provide a kind of stalk Fabrication of High Specific Capacitance (dress pot density) to fill the method for pot hydrolysis, to solve the low problem of hydrolysis device service efficiency further.
Another object of the present invention, is a kind of method providing rapid pickling, to solve the pickling problem without the stalk pulverized.
Technical scheme provided by the invention is as follows:
A hydrolysis process for treating for lignocellulose, comprises the steps:
A, raw material through overcompression, be squeezed into block, then raw material block is loaded in hydrolytic decomposition pot;
B, raw material in hydrolytic decomposition pot rapid pickling to soaking into;
C, eliminating free acid, pass into the raw material of steam to pickling and be hydrolyzed.
Described compression, can extrude bundling by extruder, can be also compression molding, convenient operation during such tinning, and the charge amount effectively improving hydrolytic decomposition pot.Extruder can adopt spiral squeezing type, also can be squeeze formula.Stalk material is tied, and can be square, rectangle or cylindrical etc.
Preferably, before described raw material compression with compression after volume ratio be 1.1-10:1. more preferably, be 2-5:1.The ratio of compression, according to circumstances, after compression, both can improve unit tinning amount, not cause again too large impact to pickling speed.
Particularly, described raw material is maize straw, and the density after its compression can be 0.2-0.5g/cm3.More preferably, the density 0.25-0.35g/cm3 after its compression.
Particularly, described raw material is bagasse, the density 0.1-0.5g/cm3 after its compression.More preferably, the density 0.2-0.3g/cm3 after its compression.
When described raw material is sugarcane leaf, boiling in advance or stack retting process before its compression.This is because the special construction of sugarcane leaf surface is unfavorable for pickling, after boiling in advance or stack retting process process, can improve pickling speed.
As required, in step a, raw material of the present invention can block, the spherical shape of boil down to or spheroid, pie, cylindric, cone-shaped or other any applicable shape.Such as, raw material can be compressed into the square of 10-30cm × 10-30cm × 10-30cm.
Preferably, if described raw material is the material of the not easily pickling such as sugarcane leaf, boiling in advance or stack retting process before its compression.
In the preferred embodiment, the rapid pickling method described in step b is: after material loads hydrolytic decomposition pot, processes by one of at least following method:
(1) vacuum pickling: hydrolytic decomposition pot vacuumizes, then injecting acid solution to soaking full with substance, maintaining normal pressure pickling and soaking into material; Or
(2) vacuum-pressurization pickling: material vacuumizes rear injection acid solution, and directly pump up to 0.1-2.0MPa pickling and soak into material; Or
(3) pressurization pickling: entering acid solution by infusion after charging has acid liquor overflow to hydrolytic decomposition pot overfall, then maintains hydraulic pressure 0.15-2.0MPa and soaks into material; Or
(4) transformation pickling: infusion enters acid solution has acid liquor overflow to overfall, closes spill valve, continues infusion acid solution and dimension pressure 0.1-2.0MPa, opens overfall emptying after soaking certain hour; When pressure in tank is close to 0, (0.001-0.03MPa) starts the acid of acid filling infusion again, again closes spill valve when overfall has acid liquor overflow, continues with infusion acid and dimension pressure 0.1-2.0MPa certain hour, again emptying, the acid filling of pressure relief; Or
(5) alternating temperature pickling: fill in the hydrolytic decomposition pot of material, first passes into Steam Heating material to 50-100 DEG C, then injects acid solution to soaking full with substance.
Preferably, the pickling time of aforementioned (1) is 0.2-3h.
Preferably, the pickling time of aforementioned (2) is 0.5-1.5h.
Preferably, the pickling time of aforementioned (3) is 1.5-3h.
Preferably, dimension pressure time first time of aforementioned (4) is 0.5-2h; The second time dimension pressure time is 0.5-2h.
Preferably, the logical steaming time described in aforementioned (5) is 20min-2h.More preferably, the logical steaming time described in aforementioned (5) is 30min-1h.
Preferably, the acid liquor temperature described in aforementioned (5) is 0-30 DEG C.
Preferably, described steam pressure is 0.1-1.0MPa.More preferably, described steam pressure is 0.15-0.30MPa.
Preferably, the time of described logical steam is 1-8h.More preferably, the time of described logical steam is 2-5h.
Stalk of the present invention is the general name of remaining stem after ripe gramineae crop has gathered in the crops seed, leaf, fringe part.Preferably, stalk of the present invention, except comprising corncob, bagasse, also comprises the raw materials such as sugarcane leaf, maize straw.
Raw material directly drops in hydrolytic decomposition pot by the present invention, after pickling, gets rid of free acid, and recycling Steam Heating, is hydrolyzed to stalk.Method of the present invention, eliminates the large workload that conventional method needs to be carried out by stalk pulverizing, eliminates a large amount of man power and materials.Pickling of the present invention and hydrolysis, all in hydrolytic decomposition pot, with traditional first pickling in pickling pond, then pick up the mode of tinning hydrolysis, eliminate pickling pond, and eliminate huge manpower and equipment.
The present invention utilizes the acid solution be dipped in raw tissue, is hydrolyzed by Steam Heating, and after raw material hydrolysis, hydrolyzate squeezes out by the mode of available squeezing from raw tissue.Because logical steam is front-seat except free acid, the sulfuric acid concentration of hydrolysis material leaching liquor is relatively low, and hydrolysate relative concentration is higher, facilitates follow-up production.Such as when producing wood sugar, the hydrolyzate of this low acid, high sugar, after clarification, directly can be with acid to be concentrated into total solubility thing and reach more than 60%.In concentrate, a large amount of impurity of Precipitation, comprises lignin, calcium salt etc., dramatically reduces follow-up purifying process burden.The hydrolyzate of liquid phase process gained then can not directly be concentrated to so high concentration, because its Initial sugar concentration is very low, concentrate is made to reach the sugared concentration of more than 60%, at least need concentrated more than 10 times.Correspondingly, acid solution also concentrates 10 times, and high concentrated acid can produce strong destruction to glucide, reduces product yield.
The present invention is further, first through overcompression before tinning at raw material, can make traditionally because the volume density of material own is too low, cause hydrolytic decomposition pot charge amount very little, equipment utilization ratio is too low, and be difficult to use in commerciality hydrolysis produce raw material, as thus make sugarcane leaf, maize straw etc., be also provided with business hydrolysis produce value.
Owing to being that raw material directly drops in hydrolytic decomposition pot and is hydrolyzed, present invention also offers a kind of method of rapid pickling, the inventive method decades of times faster than traditional pickling method, such as, corncob tradition pickling method needs the time of several days that corncob center just can be made to soak into acid solution, and after the present invention adopts rapid pickling method, the most only need 0.5h, thus in hydrolytic decomposition pot, pickling and hydrolysis can be carried out simultaneously.Without the need to building pickling pond in addition again.
The present invention can be used for the fermentability syrup that production take wood sugar as principal component, can produce crystalline xylose, xylitol further.Hydrolysate also may be used for furfural production.Cellulosic sections exists with hydrolytic residue form, can be used for producing glucose, paper fibre etc.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail; But the present invention is not limited to embodiment.
Embodiment 1
By solid: liquid=1:10, adds the sulfuric acid of 1.8% in comminuting matter, 121 DEG C of hydrolysis 90min, HPLC measure total reducing sugar and the wood sugar of hydrolyzate, are calculated as follows the productive rate of total reducing sugar and wood sugar, and in this, as the reference standard compared between different hydrolysising condition.
The total reducing sugar of table 1 different stalk dilute acid hydrolysis thing and xylose yield
The method of embodiment 2 stalk rapid pickling
The major obstacle affecting pickling speed is the air in material, if removed by the air of corncob organization internal, or carries the pressure of pickling liquid, directly acid solution is pressed into corncob inside, all should accelerates the efficiency of pickling.In the present embodiment, with the complete corncob of form for object, the pickling method that comparative study four kinds is different in 50L hydrolytic decomposition pot is to pickling effect.Method one, vacuum pickling, the hydrolytic decomposition pot being about to fill material is evacuated to-0.9Mpa, then injects acid solution (1.5% sulfuric acid) to soaking full with substance, maintains normal pressure pickling certain hour.Method two, vacuum-pressurization pickling.Material vacuumizes rear injection acid solution, and directly pumps up to 0.04Mpa pickling certain hour.Method three, pressurization pickling.Enter acid solution by infusion after charging and have acid liquor overflow to hydrolytic decomposition pot overfall, then maintain hydraulic pressure 0.2Mpa certain hour.Method four, transformation pickling.Infusion enters acid solution has acid liquor overflow to overfall, closes spill valve, continues infusion acid solution and dimension pressure 0.2Mpa, opens overfall emptying after soaking certain hour.Again start the acid of acid filling infusion when pressure in tank is close to 0, again close spill valve when overfall has acid liquor overflow, continue with infusion acid and dimension pressure 0.2Mpa certain hour, again emptying, the acid filling of pressure relief.
Contrast and experiment shows (table 2), and the effect of vacuum pickling is the most outstanding, the corncob vacuum pickling 0.5h that shape is complete, immerses 2.73 times that acid solution can reach corncob weight, close to saturated.Continue to extend vacuum pickling, or with vacuum--compared with the 0.04MPa pickling 1h that pressurizes, the amount of the acid solution immersed between them there is no very big-difference.Namely, after vacuum pickling 0.5h, there is no need pressurization or extend the pickling time.
The different pickling method of table 2 is on the impact of corncob pickling effect
The effect of pressurization pickling is the prolongation with the dimension pressure time generally, and the acid solution immersing corncob increases.When total dimension pressure time consistency, the acid solution that transformation pickling is immersed than pressurization pickling is much more.At total dimension pressure time 2h, period transformation 2 times pickling, the acid solution of immersion has reached 2.3 times of corncob weight, although still lower than the level (2.73 times) of vacuum pickling, the suction acid amount of 2.3 times can reach good hydrolysis effect.If be 1h by dimension pressure time shorten, or 1.5h, the effect of pickling and hydrolysis all can be far short of what is expected.
Although transformation pickling is consuming time more slightly longer than vacuum pickling, its power cost is low, and the simple advantage of equipment is but very outstanding.Consider pickling efficiency, the stability of the simplicity and equipment operation of technique, industrial production adopts transformation pickling should be more reasonably select.
The hydrolysis of embodiment 3 corncob routine dress pot
Obtaining the corncob conventional density dress pot of 50L hydrolytic decomposition pot, after applicable pickling method and basic hydrolysising condition, using 1t hydrolytic decomposition pot in the present embodiment instead and verify.
1t hydrolytic decomposition pot (stainless steel) one-pot material corncob (moisture about 14%) 116-120kg, transformation pickling process is substantially identical with the condition of 50L tank.Detailed process is: namely enter acid solution (1.3% sulfuric acid) by infusion after charging and flow out acid solution to overfall, closing outflow valve also continues pump acid solution to 0.2MPa, open overflow valve after dimension pressure 15min and empty to 0MPa, second time pump acid solution is to 0.2MPa and dimension presses 45min, open overflow valve and empty to 0MPa, third time, same pump tieed up pressure 1h to pressure 0.2MPa.Total dimension pressure time is the time that 2h(does not include midway step-down and boosting, three total 0.5h consuming time of buck-boost).
Pickling terminates, and releases free acid solution, deduct the free acid solution of discharge, namely draw the acid solution total amount that material sucks by the total acid solution injected bottom hydrolytic decomposition pot.The shaping corncob of moisture 14% after above-mentioned condition pickling process, suck 1.94-2.0 times that acid solution is about as much as weight of material, the acid strength of discharging after pickling remains on more than 1%.
Namely hydrolytic decomposition pot passes into steam, and steam pressure is risen to 0.2MPa after discharging free acid solution, dimension setting-out solution 2h.Hydrolysis terminates, and steam off, utilizes residual steam pressure in tank to spurt the interior material that takes the dish out of the pot.
Under this hydrolysising condition, the total reducing sugar of Corncob hydrolysate can reach 14-16%, and reach more than 2.5 times of liquid hydrolysis, xylose yield can reach 26-28%(of corncob dry weight to over dry corncob).
Embodiment 4 corncob bundling is hydrolyzed
Although, vapourous water solution embodies saves a large amount of acid (free acid) than liquid state hydrolysis, the advantage of heat (heat energy that heating free acid consumes), but the unit weight of natural shaping state corncob only has 0.12(t/m3) left and right, improve the dress pot density of hydrolysis material, effectively can improve the service efficiency of hydrolytic decomposition pot.Although corncob integer dress pot is conducive to quick acid discharge, and the advantage of steam homogeneous heating, material gap is large, the shortcoming that dress pot density low (volume density) is low.On the other hand, corncob marrow is a spongiform hollow-core construction, is also to cause integer to fill one of low density reason of pot.Pulverizing can destroy the hollow-core construction of corncob, improves its volume density, but the fine particle after pulverizing can block opening of sieve, the quick acid discharge after being unfavorable for pickling, also affects penetrating and homogeneous heating of hydrolytic process steam.
By contrast, the extrusion process of corncob appropriateness may be improve its dress pot density, keeps or improves its pickling, the possible path of hydrolysis property.First, the squeeze and destroy hollow-core construction of integer corncob, also destroys corncob surface and is bordering on cellular concaveconvex structure, material itself is organized finer and close, and material block is to each other apart from more close, and overall volume density obviously increases.Secondly, extruding can make corncob be out of shape, and tissue density reaches unanimity, and namely original open texture becomes relatively fine and close, and original natural compact tissue then cracks, and becomes relatively loose, makes pickling relatively easy.3rd, extrusion process keeps the block structure of material substantially, can not produce tiny powder, can not affect pickling and acid discharge operates, and keeps heating steam in the good penetration of storeroom.
In the present embodiment, with homemade screw extrusion baler, dry corncob is extruded, obtain the wide * of long * high=19cm × 17.5cm × 18cm, weight be about 1.8kg (density is about 0.3g/cm3) corncob bundle.The hydrolytic decomposition pot of aforementioned 1t, every tank can fill 107 bundle corncobs, and weight is about 192--197kg, is 1.6 times of conventional dress pot amount (120kg).The result of pickling and hydrolysis all confirms, the corncob processed under this extruding condition, still can keep enough spacious liquid and steam penetration channel, still have the pickling good like that of integer corncob, acid discharge and hydrolysis property between material.In pickling, acid discharge, when hydrolysising condition is identical, the corncob xylose yield of bundling dress pot hydrolysis, obviously do not reduce (only 1%) than conventional dress pot density, but feed throughput significantly increases, the overall production efficiency of wood sugar will increase substantially (table 3) thereupon.Carrying out extrusion process to raw material, is obviously the effective means improving hydrolytic decomposition pot service efficiency.
Table 3 extrudes bundling fills pot density and hydrolysis effect impact on corncob
Get the mean value of three pots.
Embodiment 5 bagasse bundling steam state is hydrolyzed.
The bagasse dress pot density of nature loose condition (of surface) is very low, and general dress pot density can only reach 0.05-0.06t/m3, but the acid solution consumption of aqueous water solution preocess can not reduce.So bagasse hydrolyzate prepared by conventional liquid hydrolysis process, xylose concentration generally can only reach 2--3%, and high subsequent concentration expense occupies the major part of bagasse hydrolyzate cost.Bagasse baler is broken into 19cm × 17.5cm × 18cm by the present embodiment, and density is about the bagasse bale of 0.23g/cm3, and average over dry substance is about 1.36kg/ bundle.1t hydrolytic decomposition pot can throw this bagasse bale 83, amounts to over dry bagasse 113kg, and immediate shipment pot density reaches 0.11t/cm3, and this is doubled than loose condition (of surface) dress pot density.
Bagasse specific area is large, so pickling speed is more faster than corncob.Bagasse bale transformation pickling 2 times, total dimension pressure time 30min, acid solution immersion amount can reach about 1:2.
With the acid concentration same with corncob and hydrolysising condition, bagasse steam state hydrolyzate total sugar concentration can reach 8% (table 4), be almost 3 times of conventional liquid hydrolysis xylose concentration, and xylose yield also reaches the high level of dry weight 21%.
The wood sugar yield of table 4 bagasse bundling steam state hydrolysis and purity
*1t hydrolytic decomposition pot.Xylo-oligosaccharide is contained in xylose yield.
Embodiment 6 sugarcane top steam state is hydrolyzed
Sugarcane leaf is the accessory substance of a kind of cane sugar manufacture industry almost do not developed at present, embodiment 4 but show the analysis result (table 1) of its dilute acid hydrolysis thing, and it has the xylose production raw material that commercial development is worth.In the present embodiment, employ natural air drying sugarcane leaf (common material), and through sugarcane leaf two kinds of raw materials of stack retting.Two kinds of material all break into the sugarcane leaf bundle of 19cm × 17.5cm × 18cm, and average over dry substance 1.20kg/ ties, and 1t hydrolytic decomposition pot can throw this bagasse bale 83, amounts to over dry sugarcane leaf and is about 100kg,
After bundling sugarcane leaf loads 1m3 hydrolytic decomposition pot, by two kinds of diverse ways, the sulfuric acid with 1.3% carries out pickling process.
Pickling method 1, the program pickling of " acid filling dimension pressure-emptying decompress(ion) ", that is: hydrolytic decomposition pot top acid filling is until pressure reaches 0.2MPa---→ dimension pressure (15min)---→ and emptying from top,---→ second time acid filling is to 0.2MPa---→ dimension pressure (15min)---→ and emptying, acid discharge.
Pickling method 2, heat steams cold soaking, that is: pass into steam from hydrolytic decomposition pot top, and cold air discharged by bottom valve.There is steam to emerge to bottom valve, close bottom valve and overhead vapor, and inject cold acid solution (20 DEG C) and have acid solution to flow into tank top overfall, maintain 10 minutes, drain free acid solution from bottom.
Table 5 sugarcane leaf ties different pickling programs inhales acid impact on material
*the sugarcane leaf amount of in bundling, 97-99kg, sulfuric acid 1.1-1.3%.
As shown in Table 5, after 2 picklings of fresh siccative transformation, suck acid solution and reach 260L, and the suction acid amount that stack retting material only needs transformation pickling once can reach identical.But, if fresh siccative adopts after Steam Heating carry out pickling again, the pickling effect of transformation 2 times also can be reached.The pickling effect of contrast different disposal is found out, boiling in advance or stack retting process, all contribute to deface structure, accelerates the immersion of acid solution.
Adopt the sulfuric acid concentration that bagasse, corncob are same, hydrolysising condition, sugarcane top at the xylose yield about 19 ~ 21% of 1m3 hydrolytic decomposition pot, between total sugar yield 24% to 27% (table 6).
The xylose yield of table 6 sugarcane top steam state hydrolysis
Obviously, sugarcane top bundling steam state is hydrolyzed, although xylose yield and sugared concentration are a little less than the highest corncob of hemicellulose level, but in consumption acid, water consumption is energy-conservation upper and corncob is the same, therefore, after applying technique of the present invention, sugarcane top possesses the value of the commercial Application preparing wood sugar completely.
Embodiment 7 maize straw bundling steam state is hydrolyzed
Maize straw stem is through tearing into silk, and stack retting process, then bundling, after bundling, plastic ties bundle watchman's wooden clapper is fixed, and makes final average external volume be 21cm × 17.5cm × 17.5cm, average over dry heavy 1.2kg, 1m
3hydrolytic decomposition pot is single pot of charging 69 bundle on average, amounts to over dry maize straw 83kg.
The pickling scheme of the steam state hydrolysis of maize straw bundle is with sugarcane leaf, and the acid strength 1%-1.1% namely after material pickling, maize straw inhales acid than (1:2.7) and sugarcane leaf (1:2.6) in same scope.
Nature after acid discharge terminates, passes into steam from the bottom of tank, and hydrolysis of boosting after row's cold air 2 times, hydrolysis pressure is 0.20MPa, and hydrolysis time is 1h.The analysis result (table 7) of hydrolyzate shows, adopt vapourous water solution in conjunction with bundling hydrolysed corn stalk, its xylose yield, total reducing sugar all can reach the degree of commercial Application.
The effect of table 7 maize straw bundling steam state dilute acid hydrolysis
Embodiment 8
The operation of the present embodiment is with embodiment 3, difference is, in the present embodiment, 1-2% phosphoric acid is adopted to replace sulphuric acid hydrolysis, under the condition of the hydrolysis pressure set, hydrolysis time, result shows, phosphoric acid solution remains on the concentration of 1-2% after material pickling, and said hydrolyzed condition can make the hydrolysis of hemicellulose of various material abundant.For corncob, hydrolyzate total reducing sugar can reach 14-16%, and reach more than 2.5 times of liquid hydrolysis, xylose yield can reach 26-28%(of corncob dry weight to over dry corncob).
Claims (7)
1. the hydrolysis process for treating of stalk hemicellulose, is characterized in that: for directly producing wood sugar, comprise the steps:
A, stalk, without pulverizing, through overcompression, are squeezed into block, then load in hydrolytic decomposition pot by raw material block;
B, raw material in hydrolytic decomposition pot rapid pickling to soaking into;
C, eliminating free acid, pass into the raw material of steam to pickling and be hydrolyzed;
Wherein, the rapid pickling method described in step b is: after raw material loads hydrolytic decomposition pot, processes by one of at least following method:
(1) vacuum pickling: hydrolytic decomposition pot vacuumizes, then injecting acid solution to soaking full with substance, maintaining normal pressure pickling and soaking into material; Or
(2) transformation pickling: infusion enters acid solution has acid liquor overflow to hydrolytic decomposition pot overfall, closes spill valve, continues infusion acid solution and dimension pressure 0.1-2.0MPa, opens overfall emptying after soaking certain hour; Again start the acid of acid filling infusion when pressure in tank is close to 0, again close spill valve when overfall has acid liquor overflow, continue with infusion acid and dimension pressure 0.1-2.0MPa certain hour, again emptying, the acid filling of pressure relief; Or
(3) alternating temperature pickling: fill in the hydrolytic decomposition pot of material, first passes into Steam Heating material to 50-100 DEG C, then injects acid solution to soaking full with substance.
2. the hydrolysis process for treating of stalk hemicellulose as claimed in claim 1, is characterized in that: the volume ratio before the raw material compression described in step a and after compression is 1.1-10:1.
3. the hydrolysis process for treating of stalk hemicellulose as claimed in claim 1, is characterized in that: boiling in advance or stack retting process before the raw material compression described in step a.
4. the hydrolysis process for treating of stalk hemicellulose as claimed in claim 1, is characterized in that: the raw material boil down to described in step a is spherical, pie, cylindric or cone-shaped.
5. the hydrolysis process for treating of stalk hemicellulose as claimed in claim 1, is characterized in that: the pickling time of (1) is 0.2-3h.
6. the hydrolysis process for treating of stalk hemicellulose as claimed in claim 1, is characterized in that: dimension pressure time first time of (2) is 0.5-2h; The second time dimension pressure time is 0.5-2h.
7. the hydrolysis process for treating of stalk hemicellulose as claimed in claim 1, it is characterized in that, the logical steaming time of (3) is 20min-2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210005719.5A CN102619118B (en) | 2012-01-09 | 2012-01-09 | Hydrolytic treatment method for straw hemicellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210005719.5A CN102619118B (en) | 2012-01-09 | 2012-01-09 | Hydrolytic treatment method for straw hemicellulose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102619118A CN102619118A (en) | 2012-08-01 |
| CN102619118B true CN102619118B (en) | 2015-03-11 |
Family
ID=46559302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210005719.5A Active CN102619118B (en) | 2012-01-09 | 2012-01-09 | Hydrolytic treatment method for straw hemicellulose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102619118B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091689A (en) * | 1993-03-03 | 1994-09-07 | 范德家 | The method that the vacuum pressed dipping is produced difficult firebrand material |
| US5972118A (en) * | 1995-10-27 | 1999-10-26 | Tennessee Valley Authority | Concentrated sulfuric acid hydrolysis of lignocellulosics |
| CN1458334A (en) * | 2003-05-23 | 2003-11-26 | 江立 | Presteaming process for plant fiber material in steam explosion pulping |
| CN1858043A (en) * | 2006-06-07 | 2006-11-08 | 济南圣泉集团股份有限公司 | Method for producing furol by extruding plant stalk |
| CN101880329A (en) * | 2009-05-04 | 2010-11-10 | 陈培豪 | Method for preparing plant hemicellulose hydrolysis liquid and method for extracting xylose and gum sugar |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7198925B2 (en) * | 2004-09-30 | 2007-04-03 | Iogen Energy Corporation | Pre-treatment of bales of feedstock |
| WO2011103180A2 (en) * | 2010-02-16 | 2011-08-25 | Grain Processing Corporation | Process for hydrolysis of wet fiber and method for producing fermentation products from wet fiber |
-
2012
- 2012-01-09 CN CN201210005719.5A patent/CN102619118B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091689A (en) * | 1993-03-03 | 1994-09-07 | 范德家 | The method that the vacuum pressed dipping is produced difficult firebrand material |
| US5972118A (en) * | 1995-10-27 | 1999-10-26 | Tennessee Valley Authority | Concentrated sulfuric acid hydrolysis of lignocellulosics |
| CN1458334A (en) * | 2003-05-23 | 2003-11-26 | 江立 | Presteaming process for plant fiber material in steam explosion pulping |
| CN1858043A (en) * | 2006-06-07 | 2006-11-08 | 济南圣泉集团股份有限公司 | Method for producing furol by extruding plant stalk |
| CN101880329A (en) * | 2009-05-04 | 2010-11-10 | 陈培豪 | Method for preparing plant hemicellulose hydrolysis liquid and method for extracting xylose and gum sugar |
Non-Patent Citations (3)
| Title |
|---|
| 木材水解新工艺的研究;谢明德等;《化学世界》;19640214(第2期);第59页-62页 * |
| 速生杉木木材液体渗透性及影响因子;马掌法等;《浙江林学院学报》;20010930;第18卷(第3期);第278页-280页 * |
| 高温液态水/蒸汽渗透-酶法处理麦草秸秆的工艺研究;田毅红等;《农产品加工·学刊》;20080228(第127期);第65页-67页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102619118A (en) | 2012-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100999739B (en) | Process for treating straw by vapour explosive and alkaline oxydol oxydizing | |
| CN110978171B (en) | Preparation method and application of bamboo pulp fiber and bamboo extract from bamboo | |
| CN104271752A (en) | Method for processing a biomass containing lignocellulose | |
| CN103589185B (en) | Method for extracting pigment and polyphenol from water chestnut peels | |
| CN109653012B (en) | Method for preparing dissolving pulp by using straws or energy plants | |
| CN103898780A (en) | Biomass treatment method | |
| CN103519297B (en) | High-efficiency energy-saving processing method of sweet potato juice | |
| CN103320476A (en) | Method and technology for high-value comprehensive utilization of banana stems and leaves | |
| CN102586494B (en) | Hydrolytic treatment method of hemicellulose raw material | |
| CN101492892B (en) | Method for producing paper-pulp by using cotton stalk core or kendir stalk core | |
| WO2019196165A1 (en) | Method for continuously separating lignocellulose component | |
| CN101591688A (en) | But a kind of method of obtaining conversion of substrate by the bacterium chaff | |
| CN102644210A (en) | Method for pretreating biomass through microwave coupling high boiling alcohol | |
| CN102321993B (en) | Pretreatment method for biomass fiber material | |
| CN102559942B (en) | Hydrolysis treatment method of straw hemicellulose | |
| CN105039460B (en) | A kind of bamboo particle pretreatment method and its application in enzymatic saccharification | |
| CN102619118B (en) | Hydrolytic treatment method for straw hemicellulose | |
| CN102206928A (en) | Method for blasting plant biomass walls with oxygen | |
| CN102586495B (en) | Rapid pickling and hydrolytic treatment method of straws | |
| CN106589156A (en) | Agaric polysaccharide extraction method | |
| CN1081651C (en) | Process for preparing humic acid by aerating stalks | |
| CN103694371B (en) | A kind of preparation method of hovenia polysaccharides | |
| CN102350265A (en) | Methods for raising homogeneity of steam exploded material | |
| CN110669875B (en) | Comprehensive utilization method for extracting xylose from plants by chemical mechanical method | |
| CN103584233A (en) | High-sugar-degree sweet potato juice and method for processing high-sugar-degree sweet potato juice |
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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180118 Address after: Xinyang Street Park Road, Haicang District of Xiamen city of Fujian Province, No. 10 361000 Patentee after: THOMSON BIOTECH Address before: Siming District seven road Xiamen 361000 Fujian province No. 1 25 floor Patentee before: ZHONGDERUI BIOREFINERY LAB XIAMEN Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230506 Address after: 3rd floor, No.10-1 Xinyuan South Road, Haicang District, Xiamen City, Fujian Province, 361000 Patentee after: Gu Chuangxin Biotechnology (Xiamen) Co.,Ltd. Address before: 361000 10 Xinyuan South Road, Xinyang street, Haicang District, Xiamen, Fujian Patentee before: THOMSON BIOTECH |