CN102619118A - Hydrolytic treatment method for straw hemicellulose - Google Patents
Hydrolytic treatment method for straw hemicellulose Download PDFInfo
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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 that ripe gramineae crop has been gathered in the crops the seed general name of remaining stem, leaf, fringe part afterwards; Also comprise and press sugar bagasse afterwards; 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 the cellulose hydrolysis product is glucose (hexose), and the hydrolysis of hemicellulose product is mainly wood sugar, arabinose (being pentose), and the lignin degradation thing is the compound that contains phenyl ring of a series of complicacies.
Stalk hemicellulose partly is easy to by dilute acid hydrolysis, and generating with pentose (wood sugar, arabinose) is the hemicellulose hydrolysate of main component.Can directly prepare the functional sweetener crystalline xylose after hemicellulose dilute acid hydrolysis thing is purified; Arabinose; Or directly the wood sugar in the hydrolysate is reduced to the higher functional sweetener xylitol of added value through biofermentation, perhaps xylose-fermenting production comprises all kinds of chemical products of alcohol fuel.In addition, the wood sugar in the hemicellulose hydrolysate also can generate the important chemical material furfural through dehydration.Although stalk resource is very abundant, hemicellulose wherein will obtain cheap hemicellulose hydrolysate not a duck soup also very easily by dilute acid hydrolysis.Because stalk is bulky, volume density is low, and traditional method for hydrolysis not only steam, acid solution consumption is big, and the hydrolysis device utilization ratio is also very low.Simultaneously, the acid solution of hydrolytic process consumption finally gets into environment, and the acid solution consumption is big more, and the environmental improvement burden of stalk hydrolysis factory is just heavy more.Therefore, according to existing half fiber hydrolysis process, no matter be furfurol industry, or wood sugar (alcohol) industry, all produce and be difficult to waste water, the waste residue administered in a large number, belong to typical high energy consumption, heavy polluted industry.
The technology for preparing wood sugar with traditional dilute acid hydrolysis method hydrolysis of corncob, bagasse hemicellulose is example, and raw material is packed into after the hydrolysis kettle, adds sulfuric acid solution and also makes the terminal point sulfuric acid concentration reach 1-1.5%, feeds steam, hydrolysis 1.5-2h under the 115--130 ℃ of condition.The hydrolyzate sugar content that the hydrolysis end promptly leaches is different because of raw material, approximately between the 2.5-6%.Be to improve the rate of recovery of wood sugar, a residue must boil once with clear water usually again in jar, and water cooking liquid contains the about 1-2% of sugar, is used for the hydrolysis of next group material after supplying acid.Not only the hydrolytic process power consumption is big for the liquid hydrolysis process of this stalk hemicellulose, and gained hydrolyzate sugar concentration is also very low.With the corncob is example, and the total sugar concentration of liquid hydrolyzate generally is no more than 6%, and the total sugar concentration of the liquid hydrolyzate of bagasse even very difficult above 3%.Cross low sugared concentration and increased follow-up concentrated burden.
In fact, have only the acid of immersing the stalk organization internal to be only the effective acid of participating in catalytic hydrolysis reaction, the free acid solution in material gap belongs to the invalid acid of not participating in reaction.With corncob; The stalk that this type of bagasse has been widely used in hydrolysis is an example; The voidage that they are piled up naturally generally surpasses 50%, and the free acid solution that is in the gap has not only been wasted heat energy, has also diluted the sugared concentration of hydrolyzate; Increase the concentrated expense in later stage, increased the weight of the burden of hydrolyzate purification and environmental improvement simultaneously.
If the stalk tissue soaks into acid solution, as long as obtain and the same temperature conditions of liquid hydrolysis, the acid hydrolytic reaction of stalk obviously can carry out equally.Steam is to obtain and the same effective media of temperature conditions of liquid hydrolysis, soaks into stalk hydrolysis under the steam state condition of acid solution, obviously just can avoid many defectives of liquid hydrolysis, reduces stalk hydrolysis production cost significantly.But stalk is organized dense, and institutional framework is without the stalk that destroys and be not easy to soak into very soon acid solution.For example, complete corncob needs time a couple of days just can soak into acid solution usually.Humans such as Luo Peng 0.5% dilute sulfuric acid soaks through cutting off wheat straw raw material, and the processing time still needs 12 hours.(Luo Peng Liu Zhong king promotion, acid catalyzed steam blasting preliminary treatment intensity is to the research of wheat straw enzyme hydrolysis influence.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, and it is infeasible in actual production, to become.
Pulverize stalk, acid solution is sprayed onto on the comminuting matter again, because contact-making surface enlarges, acid solution diffusion length shortens, and also can play the effect of quickening pickling.For example; People such as Zhao Hui are sprayed to the surface of crushing maize core with 15% sulfuric acid, soak into certain hour, use the Steam Heating hydrolysis again; The hemicellulose hydrolysate reducing sugar degree of depth of being extracted can reach 13% (Zhao Hui Wu state peak Zhang Kechang, corncob hemicellulose normal pressure acid hydrolysis Study on Technology.Heilongjiang University's natural science journal, 2003,20 (1), 118-12).But stalk is pulverized before must be through dried, and crushing process also needs consumption of power, spray acid, and the process of pulverizing also need take a large amount of places and equipment.This has obviously improved the production cost of stalk hydrolysis.
Carry out the steam state acid hydrolysis if can utilize, just can remove the loaded down with trivial details process of raw material pulverizing from without the stalk of pulverizing.But, must can realize quick pickling, utilization is carried out the acid-hydrolyzed technology of steam state without the stalk of pulverizing just has actual application value.If can further improve the dress pot density of stalk at hydrolytic decomposition pot on this basis, this steam state benefit that hydrolysis process is brought into play is that the conventional liquid hydrolysis process is incomparable.
Summary of the invention
One of the object of the invention; Be to provide the method for the stalk of the broken processing of a kind of steam state hydrolysis untreated powder, low excessively with sugared concentration after the hydrolysis that solves background technology, invalid acid solution is too much; Waste heat energy and later stage concentrate problems such as expense, and this loaded down with trivial details operation of pulverizing that economizes in raw materials.
Another object of the present invention is to provide the high specific volume of a kind of stalk (dress pot density) to adorn the method for pot hydrolysis, with the low problem of further solution hydrolysis device service efficiency.
A purpose more of the present invention is to provide a kind of method of quick pickling, to solve the pickling problem without the stalk of pulverizing.
Technical scheme provided by the invention is following:
A kind of hydrolysis process for treating of lignocellulose comprises the steps:
A, raw material through overcompression, be squeezed into piece, then raw material block is packed in the hydrolytic decomposition pot;
B, raw material in hydrolytic decomposition pot fast pickling to soaking into;
C, eliminating free acid, feeding steam is hydrolyzed to the raw material of pickling.
Described compression, can extruder the extruding bundling, also can be compression molding, be convenient to operate during tinning like this, and effectively improve the charge amount of hydrolytic decomposition pot.Extruder can adopt spiral squeezing type, also can be the hydraulic pressure squash type.The stalk material is tied, and can be square, rectangle or cylindrical etc.
Preferably, before the compression of described raw material with compression after volume ratio be 1.1-10:1. more preferably, be 2-5:1.The ratio of compression according to circumstances, after the compression, both can improve unit tinning amount, and pickling speed is not caused too big influence again.
Particularly, described raw material is a 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 a 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 was the sugarcane leaf, boiling in advance or stack retting were handled before its compression.This is that boiling in advance or stack retting can improve pickling speed after handling because the special construction of sugarcane leaf surface is unfavorable for pickling.
As required, among the step a, raw material of the present invention is can boil down to block, spherical shape or spheroid, pie, cylindric, cone-shaped or other any suitable shape.For example, raw material can be compressed into the square of 10-30cm * 10-30cm * 10-30cm.
Preferably, be difficult for the material of pickling if described raw material is a sugarcane leaf etc., boiling in advance or stack retting are handled before its compression.
In preferred embodiment of the present invention, the described quick pickling method of step b is: material is packed into behind the hydrolytic decomposition pot, handles with one of following at least method:
(1) vacuum pickling: hydrolytic decomposition pot vacuumizes, and injects acid solution then to soaking full with substance, keeps normal pressure pickling to material and soaks into; Or
(2) vacuum-pressurization pickling: material vacuumizes the back and injects acid solution, and directly pumps up to 0.1-2.0MPa pickling to material and soak into; Or
(3) pressurization pickling: acid solution to hydrolytic decomposition pot overfall is injected with pump in charging back has acid solution to overflow, and keeps hydraulic pressure 0.15-2.0MPa then and soaks into to material; Or
(4) transformation pickling: pump injects acid solution to overfall has acid solution to overflow, and closes spill valve, and acid solution annotated by the continuation pump and dimension is pressed 0.1-2.0MPa, opens the overfall emptying behind the immersion certain hour; (0.001-0.03MPa) starts once more and annotates sour pump and annotate acid when the jar internal pressure is close to 0, when overfall has acid solution to overflow, closes spill valve once more, continues to annotate acid and dimension is pressed the 0.1-2.0MPa certain hour with pump, pressure relief emptying once more, annotates acid; Or
(5) alternating temperature pickling: fill in the hydrolytic decomposition pot of material, feed the Steam Heating material earlier, inject acid solution then to soaking full with substance to 50-100 ℃.
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, tieing up the pressure time first time of aforementioned (4) is 0.5-2h; For the second time tieing up the pressure time is 0.5-2h.
Preferably, aforementioned (5) described logical steam time is 20min-2h.More preferably, aforementioned (5) described logical steam time is 30min-1h.
Preferably, aforementioned (5) described acid liquor temperature is 0-30 ℃.
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 that ripe gramineae crop has been gathered in the crops the seed general name of remaining stem, leaf, fringe part afterwards.Preferably, stalk of the present invention also comprises raw materials such as sugarcane leaf, maize straw except that comprising corncob, bagasse.
The present invention directly drops into raw material in the hydrolytic decomposition pot, after the pickling, gets rid of free acid, utilizes Steam Heating again, and stalk is hydrolyzed.Method of the present invention has been saved the big workload that conventional method need be pulverized stalk, has saved great amount of manpower and material resources.Pickling of the present invention and hydrolysis all in hydrolytic decomposition pot, with traditional elder generation's pickling in the pickling pond, pick up the mode of tinning hydrolysis again, have saved the pickling pond, and have saved huge manpower and equipment.
Utilization of the present invention is dipped in the acid solution in the raw tissue, and through the Steam Heating hydrolysis, after the raw material hydrolysis, the mode of available squeezing pushes hydrolyzate to come out from raw tissue.Because logical steam front row is except free acid, the sulfuric acid concentration of hydrolysis material leaching liquor is relatively low, and hydrolysate concentration is higher relatively, convenient follow-up production.For example when producing wood sugar, the hydrolyzate of this low acid, high sugar can directly be with acid to be concentrated into total solubility thing and reach more than 60% after clarification.Deposition is separated out a large amount of impurity in the concentrate, comprises lignin, and calcium salt etc. have greatly alleviated 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 sugared concentration is very low, make concentrate reach the sugared concentration more than 60%, need concentrate more than 10 times at least.Correspondingly, acid solution has also concentrated 10 times, and high concentrated acid can produce strong destruction to glucide, has reduced product yield.
The present invention is further; Elder generation before tinning can make traditionally because the volume density of material own is too low through overcompression at raw material, causes the hydrolytic decomposition pot charge amount very little; The equipment utilization ratio is too low; And be difficult to use in the raw material that commercial hydrolysis is produced, thereby, also had the value that commercial hydrolysis is produced as making sugarcane leaf, maize straw etc.
Owing to be that raw material directly drops into hydrolysis in the hydrolytic decomposition pot; The present invention also provides a kind of method of quick pickling, and the inventive method is than fast tens of times of traditional pickling method, for example; Corncob tradition pickling method needs several days time just can make the corncob center soak into acid solution; And the present invention adopts after the quick pickling method, and the fastest needs 0.5h, thereby can in hydrolytic decomposition pot, carry out pickling and hydrolysis simultaneously.Need not to build in addition again the pickling pond.
It is the fermentability syrup of principal component that the present invention can be used for producing with the wood sugar, further can produce crystalline xylose, xylitol.Hydrolysate also can be used for furfural production.The cellulose part exists with the hydrolytic residue form, can be used for producing glucose, paper fibre etc.
The specific embodiment
Below in conjunction with embodiment the present invention is done further explain; But the present invention is not limited to embodiment.
Embodiment 1
By solid: liquid=1:10, add 1.8% sulfuric acid in the comminuting matter, 121 ℃ of hydrolysis 90min, HPLC measures the total reducing sugar and the wood sugar of hydrolyzate, calculates the productive rate of total reducing sugar and wood sugar by following formula, and with this as the reference standard that compares between the different hydrolysising conditions.
The total reducing sugar and the wood sugar productive rate of the different stalk dilute acid hydrolysis of table 1 thing
The method of the quick pickling of embodiment 2 stalks
The major obstacle that influences pickling speed is the air in the material, if the air of corncob organization internal is removed, perhaps carries the pressure of pickling liquid, directly acid solution is pressed into corncob inside, all should quicken the efficient of pickling.In the present embodiment, be object with the corncob of complete form, in the 50L hydrolytic decomposition pot comparative study four kinds of different pickling methods to the pickling effect.Method one, the vacuum pickling, the hydrolytic decomposition pot that is about to fill material is evacuated to-0.9Mpa, injects acid solution (1.5% sulfuric acid) then to soaking full with substance, keeps normal pressure pickling certain hour.Method two, vacuum-pressurization pickling.Material vacuumizes the back and injects acid solution, and directly pumps up to 0.04Mpa pickling certain hour.Method three, the pressurization pickling.Acid solution to hydrolytic decomposition pot overfall is injected with pump in the charging back has acid solution to overflow, and keeps hydraulic pressure 0.2Mpa certain hour then.Method four, the transformation pickling.Pump injects acid solution to overfall has acid solution to overflow, and closes spill valve, and acid solution annotated by the continuation pump and dimension is pressed 0.2Mpa, opens the overfall emptying behind the immersion certain hour.Start to annotate sour pump once more and annotate acid when the jar internal pressure is close to 0, when overfall has acid solution to overflow, close spill valve once more, continue to annotate acid and dimension is pressed the 0.2Mpa certain hour, pressure relief emptying once more, annotate acid with pump.
Contrast and experiment shows (table 2), and the effect of vacuum pickling is the most outstanding, the corncob vacuum pickling 0.5h of shape intact, and the immersion acid solution can reach 2.73 times of corncob weight, near saturated.Continue to prolong the vacuum pickling, or with vacuum--pressurization 0.04MPa pickling 1h compares, and the amount of the acid solution that immerses between them does not have very big-difference.Be after the vacuum pickling 0.5h, there is no need pressurization or prolong the pickling time.
The different pickling methods of table 2 are to the influence of corncob pickling effect
The effect of pressurization pickling is the prolongation with the dimension pressure time generally, and the acid solution that immerses corncob increases.Under the situation of total dimension pressure time unanimity, the acid solution that the transformation pickling is immersed than the pressurization pickling is much more.At total dimension pressure time 2h, during the pickling of transformation 2 times, the acid solution of immersion has reached 2.3 times of corncob weight, though still be lower than the level (2.73 times) of vacuum pickling, 2.3 times suction acid amount can reach good hydrolysis effect.Shorten to 1h if will tie up the pressure time, or 1.5h, the effect of pickling and hydrolysis all can be far short of what is expected.
Though the transformation pickling is consuming time slightly more longer than vacuum pickling, its power cost is low, and the simple advantage of equipment is but very outstanding.Take all factors into consideration pickling efficient, the simple and direct property and the operation stability of equipment of technology, it should be more reasonably to select that commercial production adopts the transformation pickling.
The hydrolysis of the conventional dress pot of embodiment 3 corncobs
At the conventional density dress of the corncob pot of acquisition 50L hydrolytic decomposition pot, after pickling method that is suitable for and the basic hydrolysising condition, use the 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, the condition of transformation pickling process and 50L jar is basic identical.Detailed process is: promptly inject acid solution (1.3% sulfuric acid) to overfall with pump after the charging and flow out acid solution; Closing outflow valve also continues the pump acid solution to 0.2MPa; Open overflow valve behind the dimension pressure 15min and empty to 0MPa; The pump acid solution is pressed 45min to 0.2MPa and dimension for the second time, opens overflow valve and empties to 0MPa, and same for the third time pump to pressure 0.2MPa dimension is pressed 1h.Total dimension pressure time is 2h (time that does not include step-down midway and boost, three total 0.5h consuming time of buck-boost).
Pickling finishes, and emits free acid solution from the hydrolytic decomposition pot bottom, uses total acid solution of injecting to deduct the free acid solution of discharge, promptly draws the acid solution total amount that material sucks.Moisture 14% shaping corncob is after above-mentioned condition pickling is handled, and the acid solution that sucks is about as much as 1.94-2.0 times of weight of material, and the acid strength of discharging after the pickling remains on more than 1%.
Hydrolytic decomposition pot promptly feeds steam, and steam pressure is risen to 0.2MPa after discharging free acid solution, and the dimension setting-out is separated 2h.Hydrolysis finishes, and steam off utilizes jar interior residual steam pressure to spurt the interior material that takes the dish out of the pot.
Under this hydrolysising condition, the total reducing sugar of corncob hydrolyzate can reach 14-16%, reaches more than 2.5 times of liquid hydrolysis, and the wood sugar productive rate can reach 26-28% (to the over dry corncob) of corncob dry weight.
Embodiment 4 corncob bundling hydrolysis
Though; Vapourous water is separated to embody than liquid hydrolysis and is practiced thrift a large amount of acid (free acid); The advantage of heat (heat energy that the heating free acid consumes); But the unit weight of natural shaping state corncob has only about 0.12 (t/m3), improves the dress pot density of hydrolysis material, can effectively improve the service efficiency of hydrolytic decomposition pot.Though corncob integer dress pot helps the advantage of quick acid discharge and the even heating of steam, the material gap is big, the low shortcoming of dress pot density low (volume density).On the other hand, the corncob marrow is a spongiform hollow-core construction, also is to cause one of low density reason of integer dress pot.Pulverizing can destroy the hollow-core construction of corncob, improves its volume density, but the fine particle after pulverizing can stop up opening of sieve, is unfavorable for pickling quick acid discharge afterwards, also influences penetrating and evenly heating of hydrolytic process steam.
By contrast, the extrusion process of corncob appropriateness possibly be to improve its dress pot density, keeps or improves its pickling, the possible path of hydrolysis property.At first, squeeze and destroy the hollow-core construction of integer corncob, also destroyed the corncob surface and be bordering on cellular concaveconvex structure, it is more fine and close that material itself is organized, the material piece is to each other apart from more approaching, overall volume density obviously increases.Secondly, extruding can make the corncob distortion, and tissue density reaches unanimity, and it is fine and close relatively that promptly original open texture becomes, and original natural compact tissue then cracks, and becomes loose relatively, makes pickling relatively easy.The 3rd, extrusion process keeps the block structure of material substantially, can not produce tiny powder, can not influence pickling and acid discharge operation, keeps the good penetration of heating steam at storeroom.
In the present embodiment, dry corncob is pushed with homemade screw extrusion baler, must the wide * height=19cm of long * * 17.5cm * 18cm, weight is about the corncob of 1.8kg (the about 0.3g/cm3 of density) and ties.The hydrolytic decomposition pot of aforementioned 1t can be adorned 107 bundles of corncobs for every jar, and the about 192--197kg of weight is that conventional dress pot is measured (120kg) 1.6 times.The result of pickling and hydrolysis confirms, the corncob of under this extruding condition, handling still can keep enough spacious liquid and steam penetration channel between the material, still has integer corncob such good pickling, acid discharge and hydrolysis property.In pickling, acid discharge is under the identical situation of hydrolysising condition; The corncob wood sugar productive rate of bundling dress pot hydrolysis; Obviously do not reduce (only 1%) than conventional dress pot density, but the raw material treating capacity increases significantly, the overall manufacturing efficient of wood sugar will increase substantially (table 3) thereupon.Raw material is carried out extrusion process, obviously is the effective means that improves the hydrolytic decomposition pot service efficiency.
Table 3 extruding bundling is to the influence of corncob dress pot density and hydrolysis effect
Get three pots mean value.
Embodiment 5 bagasse bundling steam state hydrolysis.
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 liquid hydrolytic process can not reduce.So, the bagasse hydrolyzate of conventional liquid hydrolysis process preparation, xylose concentration generally can only reach 2--3%, and high follow-up concentrated expense has occupied the major part of bagasse hydrolyzate cost.Present embodiment breaks into 19cm * 17.5cm * 18cm with bagasse with baler, the bagasse bale of the about 0.23g/cm3 of density, and the average about 1.36kg/ of over dry substance ties.The 1t hydrolytic decomposition pot can be thrown 83 of this bagasse bales, 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.
The bagasse specific area is big, so pickling speed is much faster than corncob.Pressure time 30min is always tieed up in bagasse bale transformation pickling 2 times, and acid solution immersion amount can reach about 1:2.
Use acid concentration and the hydrolysising condition same with corncob, bagasse steam state hydrolyzate total sugar concentration can reach 8% (table 4), almost be 3 times of conventional liquid hydrolysis xylose concentration, and the wood sugar productive rate has also reached the high level of dry weight 21%.
The wood sugar yield and the purity of the hydrolysis of table 4 bagasse bundling steam state
*The 1t hydrolytic decomposition pot.Comprised xylo-oligosaccharide in the wood sugar productive rate.
Embodiment 6 sugarcane top steam state hydrolysis
The sugarcane leaf is the accessory substance of a kind of cane sugar manufacture industry of almost not developed at present, the embodiment 4 but analysis result (table 1) of its dilute acid hydrolysis thing is shown that it is to have the xylose production raw material that commercial development is worth.In the present embodiment, two kinds of raw materials of sugarcane leaf of natural air drying sugarcane leaf (common material) and process stack retting have been used.The sugarcane leaf that two kinds of material all break into 19cm * 17.5cm * 18cm is tied, and average over dry substance 1.20kg/ ties, and the 1t hydrolytic decomposition pot can be thrown 83 of this bagasse bales, amounts to over dry sugarcane leaf about 100kg,
Bundling sugarcane leaf is packed into after the 1m3 hydrolytic decomposition pot, and by two kinds of diverse ways, the sulfuric acid with 1.3% carries out the pickling processing.
Pickling method 1; The program pickling of " annotating acid dimension pressure-emptying decompress(ion) "; That is: notes acid in hydrolytic decomposition pot top reaches 0.2MPa until pressure---→ tie up and press (15min)---→ emptying from the top,---→ notes acid for the second time is to 0.2MPa---→ tie up and press (15min)---→ emptying, acid discharge.
Pickling method 2, heat is steamed cold soaking, feeds steam from the hydrolytic decomposition pot top that is:, and bottom valve is discharged cold air.Have steam to emerge to bottom valve, close bottom valve and overhead vapor, and overfall there is acid solution to flow into to the tank top to inject cold acid solution (20 ℃), keeps 10 minutes, drains free acid solution from the bottom.
Table 5 sugarcane leaf is tied different pickling programs is inhaled acid to material influence
*The sugarcane leaf amount of in bundling, 97-99kg, sulfuric acid 1.1-1.3%.
Can know by table 5, after 2 picklings of fresh siccative transformation, suck acid solution and reach 260L, and the stack retting material only need the transformation pickling once can reach identical suction acid amount.But,, also can reach the pickling effect of transformation 2 times if fresh siccative carries out pickling after adopting Steam Heating again.The pickling effect of contrast different disposal finds out that boiling in advance or stack retting are handled, and all help the deface structure, accelerates the immersion of acid solution.
Adopt bagasse, the same sulfuric acid concentration of corncob, hydrolysising condition, sugarcane top is about 19～21% at the wood sugar productive rate of 1m3 hydrolytic decomposition pot, between total sugar yield 24% to 27% (table 6).
The wood sugar productive rate of table 6 sugarcane top steam state hydrolysis
Obviously, the hydrolysis of sugarcane top bundling steam state is though wood sugar productive rate and sugared concentration are a little less than the highest corncob of hemicellulose level; But in consumption acid, water consumption is energy-conservation go up and corncob the same, therefore; After having used technology of the present invention, sugarcane top possesses the value of the commercial Application of preparation wood sugar fully.
Embodiment 7 maize straw bundling steam state hydrolysis
Maize straw stem is through tearing into silk, and stack retting is handled, bundling then, and plastic ties is tied watchman's wooden clapper and is fixed behind the bundling, and making final average external volume is 21cm * 17.5cm * 17.5cm, the heavy 1.2kg of average over dry, 1m
3Over dry maize straw 83kg is amounted in 69 bundles of the average single pot of chargings of hydrolytic decomposition pot.
The pickling scheme of the steam state hydrolysis that maize straw is tied is with the sugarcane leaf, i.e. acid strength 1%-1.1% after the material pickling, maize straw inhale acid than (1:2.7) and sugarcane leaf (1:2.6) in same scope.
After the nature acid discharge finishes, feed steam from the bottom of jar, the hydrolysis of boosting behind row's cold air 2 times, hydrolysis pressure is 0.20MPa, hydrolysis time is 1h.The analysis result (table 7) of hydrolyzate shows, adopts vapourous water to separate and combines bundling hydrolysis maize straw, and its wood sugar productive rate, 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 present embodiment is with embodiment 3; Different is in the present embodiment, to adopt 1-2% phosphoric acid to replace sulphuric acid hydrolysis; Under the condition of the hydrolysis pressure of setting, hydrolysis time; The result shows that phosphoric acid solution remains on the concentration of 1-2% after the material pickling, and the said hydrolyzed condition can make the hydrolysis of hemicellulose of various materials abundant.With the corncob is example, and the hydrolyzate total reducing sugar can reach 14-16%, reaches more than 2.5 times of liquid hydrolysis, and the wood sugar productive rate can reach 26-28% (to the over dry corncob) of corncob dry weight.
Claims (10)
1. the hydrolysis process for treating of stalk hemicellulose comprises the steps:
A, stalk through overcompression, be squeezed into piece, then raw material block is packed in the hydrolytic decomposition pot;
B, raw material in hydrolytic decomposition pot fast pickling to soaking into;
C, eliminating free acid, feeding steam is hydrolyzed to the raw material of pickling.
2. the hydrolysis process for treating of stalk hemicellulose as claimed in claim 1 is characterized in that: before the described raw material compression of step a with compression after volume ratio be 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 processing before the described raw material compression of step a.
4. the hydrolysis process for treating of stalk hemicellulose as claimed in claim 1 is characterized in that: step a raw material raw material boil down to bulk, spherical shape, spheroid, pie, cylindric or cone-shaped.
5. the hydrolysis process for treating of stalk hemicellulose as claimed in claim 1 is characterized in that, the described quick pickling method of step b is: material is packed into behind the hydrolytic decomposition pot, handles with one of following at least method:
(1) vacuum pickling: hydrolytic decomposition pot vacuumizes, and injects acid solution then to soaking full with substance, keeps normal pressure pickling to material and soaks into; Or
(2) vacuum-pressurization pickling: material vacuumizes the back and injects acid solution, and directly pumps up to 0.1-2.0MPa pickling to material and soak into; Or
(3) pressurization pickling: acid solution to hydrolytic decomposition pot overfall is injected with pump in charging back has acid solution to overflow, and keeps hydraulic pressure 0.15-2.0MPa then and soaks into to material; Or
(4) transformation pickling: pump injects acid solution to overfall has acid solution to overflow, and closes spill valve, and acid solution annotated by the continuation pump and dimension is pressed 0.1-2.0MPa, opens the overfall emptying behind the immersion certain hour; Start to annotate sour pump once more and annotate acid when the jar internal pressure is close to 0, when overfall has acid solution to overflow, close spill valve once more, continue to annotate acid and dimension is pressed the 0.1-2.0MPa certain hour, pressure relief emptying once more, annotate acid with pump; Or
(5) alternating temperature pickling: fill in the hydrolytic decomposition pot of material, feed the Steam Heating material earlier, inject acid solution then to soaking full with substance to 50-100 ℃.
6. the hydrolysis process for treating of stalk hemicellulose as claimed in claim 5, it is characterized in that: the pickling time of (1) is 0.2-3h.
7. the hydrolysis process for treating of described stalk hemicellulose as claimed in claim 5, it is characterized in that: the pickling time of (2) is 0.5-1.5h.
8. the hydrolysis process for treating of described stalk hemicellulose as claimed in claim 5, it is characterized in that: the pickling time of (3) is 1.5-3h.
9. the hydrolysis process for treating of described stalk hemicellulose as claimed in claim 5, it is characterized in that: tieing up the pressure time first time of (4) is 0.5-2h; For the second time tieing up the pressure time is 0.5-2h.
10. the hydrolysis process for treating of stalk hemicellulose as claimed in claim 5 is characterized in that, (5) described logical steam time is 20min-2h.
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