CN102382310A - Lignin co-production method by comprehensively utilizing lignocellulose resources - Google Patents
Lignin co-production method by comprehensively utilizing lignocellulose resources Download PDFInfo
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Abstract
The invention discloses a lignin co-production method by comprehensively utilizing lignocellulose resources, which includes steps of (1) removing impurities in the lignocellulose resources and smashing the lignocellulose resources, (2) catalyzing pyrohydrolysis of ultra-dilute acid, (3) washing, (4) extracting an NH3 water system, (5) blowing off and recovering NH3, and (6) separating and preparing lignin. The lignin co-production method has the advantages of high efficiency, cleaning, stability, reliability, low energy consumption and cost, no pollution and the like.
Description
Technical field
The invention belongs to biomass refining and biomass energy source domain, relate to a kind of method of lignocellulose comprehensive utilization of resources coproduction xylogen, significantly improved the comprehensive utilization ratio of lignocellulose.
Technical background
The energy that current mankind is required and platform chemical are mainly derived from fossil resources such as non-renewable oil, coal, Sweet natural gas; Yet the minimizing day by day of prospective oil; The exhaustion day by day of fossil resource, world energy sources, resource problem and environment protection are faced with baptism.It is predicted; The year two thousand twenty China's oil insufficiency of supply-demand will reach 3.6 hundred million tons; The external interdependency of oil will reach 60%, and meanwhile, a large amount of utilizations of fossil resource have produced environmental pollution and climate warming problem; Threatened existent environment of people, the development and use of the especially biomass-based resource of green renewable new forms of energy and the energy more come into one's own.Ethanol, butanols, biofuel etc. are the principal modes of biomass liquid energy material, also are the especially most probable ideal substitute of oil of fossil oil, compare with traditional energy, and they are a kind of clean energy, are again a kind of renewable energy sources.A large amount of experimental studies show, use E10 vehicle-use alcohol gasoline (being that the denatured fuel ethanol content is 10% gasoline) can make octane value improve 3%, and burning more fully, thoroughly reduces carbon monoxide emission 25%-30%, reduces Carbon emission about 10%.At present; Alcohol fuel is raw materials for production with food crop (like corn, grain in storage for years etc.) mainly; Grain is in short supply, the price increase problem becomes increasingly conspicuous because the grain resource mass consumption causes, and exploitation is the attention energetically that raw material production s-generation alcohol fuel and third generation biorefinery technology receive countries in the world with non-grain crops such as lignocelluloses.Lignocellulose is the renewable resources of rich and cheap on the earth, and its growing amount every year is up to 2 * 10
11T, and utilize the no extra CO in back
2Discharging.Carbohydrate in the lignocellulose can change platform chemical such as multiple organic acid (acetic acid, succsinic acid, levulinic acid, methylene-succinic acid, L-glutamic acid, amino-succinic acid etc.), polyvalent alcohol (sorbyl alcohol, glycerine etc.), aldehyde, furans into; Can obtain aromatic hydrocarbon (benzene,toluene,xylene) and multiple fine chemicals, resol, absorption agent, tackiness agent, dispersion agent by lignin, comprehensive utilization value is very huge.The chemistry of lignocellulose, bio-transformation are to solving the energy and shortage of resources problem, alleviating environmental pollution and have important practical significance, and the utilization of wood fiber biomass resource and process engineering thereof are mentioned consequence.The annual available lignocellulose of China is mainly derived from agriculture and forestry organic waste material, trade waste and urban waste, but remains in the lower problem of utilization ratio about 700,000,000 tons.
The comprehensive utilization of wood fiber biomass resource more and more receives both at home and abroad and paying attention to widely.The lignocellulose kind is a lot; Mainly form by Mierocrystalline cellulose (35-50%), semicellulose (about 20-35%) and xylogen (about 10-25%); Three components are through the specific mode formed stable complex construction of Steel Concrete and the high-crystallinity of cellulosic molecule of being similar to crosslinked together; Make that Mierocrystalline cellulose is difficult to be hydrolyzed, thereby increased the difficulty of utilizing and caused tooling cost to increase.Pre-treatment is the guardian technique of lignocellulose trans-utilization; It mainly is that utilization physics, chemistry, biology or comprehensive method (like the combination of the quick-fried method of vapour, liquid hot water prehydrolysis, wet oxidation process, diluted acid method or several method) are separated each component; Improve the utilization and the transformation efficiency of each component; Improve yield, reduce cost.Current have in the pre-treatment that a lot of researchs concentrate on lignocellulose raw material, and purpose is to remove xylogen and semicellulose to cellulosic provide protection with destroy the crystalline structure between the cellulose macromolecule, to improve cellulosic enzymolysis transformation efficiency.Bigger progress is being obtained aspect the research of cellulosic ethanol and the industrialization in recent years in U.S.'s (NREL, Maas section horse, Bo Yite, Du Pont's Danisco etc.), Canada (Iogen, SunOpta etc.), Brazil (Dedini etc.) and Europe (Abengoa, Inbicon etc.).
Lignocellulose liquid fuel and platform chemical fail to get into the suitability for industrialized production stage fully so far, and its major cause is the selectivity and the inferior separating effect of raw materials pretreatment, and pre-treatment and enzyme processing cost are higher, make a low multiple use.Existing all kinds of preconditioning technique exists many deficiencies, and major cause is in the research and development of preconditioning technique, to have a series of problems: (1) is to the one-component pre-treatment.Pay attention to cellulosic utilization ratio like ethanol, pulping and paper-making industry, industries such as wood sugar, Xylitol are then paid attention to the utilization ratio of semicellulose; (2) the preconditioning technique basic research dynamics of carrying out itself is not enough; (3) the pre-treatment cost is high.The notion of biorefining is derived by petroleum refining.Petroleum refining is promptly isolated various petroleum chemicalss from the crude oil of complicacy; The same chemical constitution with complicacy with oil of biomass, the technology that biorefining promptly fully utilizes each field is fuel, the energy, material, medicine, platform chemical etc. with Wood Adhesives from Biomass.Fully there are two necessity in organism-absorbing purified thought: the one, and the needs of realization lignocellulose raw material microbial transformation, the 2nd, the needs of recycling semicellulose, xylogen.Iff guarantees that half the semicellulose of cellulosic utilization and xylogen are abandoned nearly and then is difficult to realize making full use of of lignocellulose, remains high thereby make whole processing transform cost.
The effective domestic method that the selectivity degraded separates semicellulose has steam explosion, dilute acid hydrolysis, liquid high-temperature-hot-water processing etc.Steam explosion can be effectively goes out semicellulose with the xylooligosaccharides isolated in form of different molecular weight (polymerization degree), but facility investment is higher, and energy consumption is not low, is easy to generate the inhibition by product; Liquid high-temperature-hot-water also has higher energy consumption, and side reaction is often more; Dilute acid hydrolysis generally has the selectivity height, and the acid catalyzed liquid high-temperature-hot-water of yield advantages of higher, particularly ultralow density is handled, and is not only with low cost, and the aftertreatment of hydrolyzed solution and waste water is simple, environmental protection, and good development and application prospect are arranged.The cellulosic component hydrolyzable is a glucose, and glucose not only can be converted into ethanol, butanols, biofuel etc. through fermentation, also can be hydrogenated to sorbyl alcohol after CR or dehydration-hydrogenation or selective oxidation are converted into hydrogen, CO
2Or alkane or hydroxymethylfurfural etc.The semicellulose component is hydrolyzed to pentoses such as wood sugar, but the wood sugar hydrogenation obtains Xylitol, and the also oxidable furfural that obtains further is converted into levulinic acid again.Xylogen is that fundamental unit passes through ehter bond and the C-C key connecting is formed by phenylpropyl alcohol alkane mainly, can transform fine chemicals such as producing phenols, (first) benzene, synthetic resins, tackiness agent, additive, and purposes very extensively.The process for extracting of xylogen has a variety of, and alkaline process is the maximum a kind of method (Chinese patent 200910088096.0 that uses at present; 201010536656.7; 200510099747.8; 201010538484.7), xylogen is that the form with the solubility phenates exists in basic soln, when adding acid, gradates to insoluble phenol and separates out.What use in a large number in the alkaline process at present is the higher NaOH solution of concentration, and production process can produce a large amount of black liquor, and environmental pollution property is big, and neutralization needs to consume a large amount of acid, and Financial cost is higher.In addition, organic solvent method also is a kind of effective means (Chinese patent 200810058824.9; 200810123846.9; 201010109597.5), but need in the process that organic solvent reclaims to consume a lot of energy, and some losses are arranged usually, and cost is higher, and the toxicity of solvent, contaminative have also hindered its large-scale application in addition.
Summary of the invention
The objective of the invention is to present lignocellulose transform ubiquitous inferior separating effect, transformation efficiency in preparation liquid fuel and the number of chemical article route and make a low multiple use, consume and pollute greatly, defective such as industrialization potential deficiency and propose a kind of method of novel a kind of lignocellulose comprehensive utilization of resources coproduction xylogen; This method synthesis utilization ratio is high, cheaply advantage.
The technical scheme that realizes above-mentioned purpose is following:
A kind of method of lignocellulose comprehensive utilization of resources coproduction xylogen may further comprise the steps:
(1) lignocellulosic material is carried out removal of impurities, pulverization process;
(2) ultra diluted acid catalysis pyrohydrolysis: lignocellulosic material is 0.05%～0.5% inorganic acid aqueous solution for (W/W) 1: 10～40 adding concentration by solid-to-liquid ratio; Soaking at room temperature 10～60min is placed in the autoclave, hydrolysis 2～10min under 145 ℃～180 ℃ conditions; Cooling rapidly after hydrolysis is accomplished, solid-liquid separation gets hydrolytic residue and hydrolyzed solution;
(3) washing: is 1: 10～20 to add entry with the hydrolytic residue of step (2) by solid-to-liquid ratio (W/W), and repetitive scrubbing is the solubility hydrolyzate wherein, and washing times is 2～4 times, solid-liquid separation, washings with wash hydrolytic residue; The hydrolyzed solution of washings and step (2) merges, and it can be used for separation and purification and prepares the D-wood sugar, also can be used for the fermentative prodn of products such as ethanol, butanols, Xylitol, also can further produce chemical such as furfural, furans, levulinic acid through chemical conversion;
(4) NH
3The aqueous systems extracting: is 1: 8～25 and NH with the washing hydrolytic residue in the step (3) by solid-to-liquid ratio (W/W)
3Aqueous systems is mixed, and places autoclave, and in 130 ℃～190 ℃ stirring extracting 15～90min, temperature reduces the back solid-liquid separation, gets extracting residue and extract; The main cellulose component of extracting residue (semicellulose and the xylogen that still contain very small amount) can be that C6 sugar is sugared with C5 seldom through enzymic hydrolysis, and extract gets into next step processing;
(5) NH
3Stripping reclaim: in the step (4) extract of heat in 45 ℃～60 ℃ in stripping tower gas expose to the sun and remove NH
3, the NH of stripping
3Through spray absorber by water absorb ammoniacal liquor, can be back to NH
3Reuse in the aqueous systems extraction steps;
(6) lignin separation preparation: NH in step (5)
3Remaining extract after stripping reclaims adds 10% sulfuric acid and regulates pH=3.0～5.0, makes the xylogen deposition separate out, and after solid-liquid separation, drying, obtains lignin product.
Said method, can also carry out enzymic hydrolysis:
(7) enzymic hydrolysis: in the extracting residue of step (4), add an amount of 0.2mol/L acetic acid-sodium-acetate buffer; Make that extracting residue (dry weight) final concentration is 2wt%～8wt%; Add cellulase preparation simultaneously; Constant temperature stirring, enzymolysis promptly obtain saccharification liquid under 46 ℃～50 ℃ conditions, can be used for the fermentative prodn of ethanol, butanols, succsinic acid, lactic acid.
Further, described lignocellulosic material comprises bagasse, sugarcane leaf, stalk, corn cob, cornstalk.
Further, the pulverization process described in the step (1) is will be crushed to 1～5mm with kibbler or knife mill lignocellulosic material.
Further, the diluted acid described in the step (2) is any one or its mixing in the inorganic acid aqueous solutions such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid; Preferably sulfuric acid, hydrochloric acid; Optimum is sulfuric acid.NH described in the step (4)
3NH in the aqueous systems
3Concentration is 1wt%～10wt%; Be preferably 2wt%～8wt%; Most preferably be 6wt%.
Further, described solid-liquid separation is any one in vacuum filtration, centrifuging, filter press, the spinning.
Described drying is any one or its combination in vacuum-drying, air blast heated drying, the microwave vacuum drying.
Stripping tower described in the step (5) removes NH
3Process in extract pH value be to be controlled at 11.0～12.5, be preferably 11.5～12.0.
Further, described cellulase preparation is acidic cellulase or the mixture that comprises acidic cellulase, beta-glucosidase, is preferably the mixture of acidic cellulase, beta-glucosidase.The addition of described cellulase preparation is that the consumption of acidic cellulase is 10～40FPU/g extracting residue, and the consumption of beta-glucosidase is 5～20CBIU/g extracting residue.Described enzymolysis time is 24～72 hours.Described 0.2mol/L acetic acid-sodium-acetate buffer pH is 4.5～5.2, most preferably is 4.8.
The pretreatment technology of existing lignocellulosic material is regarded as single resource with raw material usually, to the one-component pre-treatment, or only pays attention to the utilization of cellulose components, or only pays attention to the utilization of hemicellulose components.Pay attention to cellulosic utilization ratio like alcohol fuel, butanols, pulping and paper-making industry; Food, chemical industries such as wood sugar, xylooligosaccharides, Xylitol, furfural, furans are then paid attention to the utilization ratio of semicellulose; Exist numerous defectives such as serious waste of resources, environmental pollution is big, transformation efficiency is low, production cost is high, make lignocellulose conversion preparation liquid fuel and platform chemical be difficult to break through the insufficient bottleneck of industrialization potential.Existing pretreatment technology uses single technique means mostly, exists many deficiencies, and semicellulose is only removed in for example independent sour pre-treatment or steam explosion or high-temperature-hot-water pre-treatment; The alkali pre-treatment removes delignification and part semicellulose; Can't reach simultaneously three big components fast, the purpose of high efficiency separation, and the enzyme usage quantity is big during hydrolysis and saccharification, saccharification efficient is low; Enzymatic hydrolyzation is usually less than 70%, and the pre-treatment cost is high.Pretreatment process of the present invention is based on the different physicochemical property and the constructional feature of semicellulose, Mierocrystalline cellulose, xylogen three components in the lignocellulose; Utilize ultra dilute acid hydrolysis pre-treatment fully to degrade, separate hemicellulose components and keep most of Mierocrystalline cellulose and xylogen simultaneously, adopt rare NH then
3Xylogen in the ultra dilute acid hydrolysis residue of aqueous systems extracting lignocellulose remains the residue into high cellulose content, adds under the concentration at lower enzyme, and its enzymatic hydrolyzation significantly increases, and has improved the conversion and the comprehensive utilization ratio of bagasse.
Compared with prior art, method provided by the invention has advantages such as high-efficiency cleaning, reliable and stable, pollution-free, less energy-consumption, low cost, comprises following several respects specifically:
(1) separation of semicellulose, xylogen makes the enzymolysis efficiency of lignocellulose and transformation efficiency increase greatly; Enzymatic hydrolyzation can reach more than 95%, and meanwhile, enzymic hydrolysis can be carried out under lower enzyme concn; Reduce the consumption of cellulase, reduced production cost.
(2) Mierocrystalline cellulose in the lignocellulose, semicellulose and xylogen have fully been separated; And then be used respectively; The operational path that proposes has very high handiness and practicality, can realize liquid fuel, meticulous or platform chemical, xylogen coproduction, and only produces single product pattern and compares; Remarkable in economical benefits increases, and industrialization prospect is considerable.
(3) cellulase preparation is except acidic cellulase, and the also extra beta-glucosidase that added has reduced that cellobiose has improved the yield and the efficient of enzymatic saccharification process to the feedback inhibition of cellulase in the enzymic hydrolysis process.
(4) diluted acid of utilization ultralow density carries out catalysis, and the hydrolysis selectivity is high, effective, and side reaction is few, and environmental pollution is little, has avoided the very complicated technology of acid recovery, has reduced cost.
(5) adopt weak ammonia extracting xylogen, it is higher not only to extract yield, and the lignin product quality is good, NH
3Can reuse, its stripping-absorption recovery process energy consumption and cost are lower, and the feature of environmental protection is good.
Embodiment
In the method for the invention, mainly may further comprise the steps: 1. ultra diluted acid catalysis pyrohydrolysis; 2. hot wash hydrolytic residue; 3. NH
3Aqueous systems high temperature extracting xylogen; 4. NH
3Stripping reclaims; 5. the extract acidizing crystal separates the preparation xylogen; 5. the enzymic hydrolysis of high cellulose content residue is a monose.Different physico-chemical properties and characteristics based on semicellulose, Mierocrystalline cellulose, xylogen three components; Lignocellulose method of comprehensive utilization of the present invention hydrolysis under the acid catalyzed hot conditions of ultralow density, isolate most of hemicellulose components; Keep most Mierocrystalline cellulose and xylogen simultaneously, utilize NH then
3Aqueous systems extracting xylogen, last residuum are the extracting residue of high cellulose content, are converted into monose through enzymic hydrolysis.The semicellulose recovery is more than 70% in the method bagasse that the present invention proposes, and the Mierocrystalline cellulose recovery is about 80%-90%, and the lignin recovery rate is more than 80%, and the cellulase hydrolysis rate generally can reach more than 90%.
The main ingredient of lignocellulosic material contains Mierocrystalline cellulose, semicellulose, xylogen, mainly comprises bagasse, sugarcane leaf, stalk, corn cob, cornstalk etc.The purpose of pulverizing is to reduce material size, increasing specific surface area, but the common operation energy consumption of mechanical disintegration is higher, takes all factors into consideration, and bagasse, sugarcane leaf, stalk, corn cob, cornstalk are crushed to 1～5mm size.
Diluted acid of the present invention is that the common acid in this area comprises any one or its mixing in the inorganic acid aqueous solutions such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid; Preferably sulfuric acid, hydrochloric acid; Optimum is a sulfuric acid.Described NH
3NH in the aqueous systems
3Concentration is 1wt%～10wt%; Be preferably 2wt%～8wt%; Most preferably be 6wt%.
Solid-liquid separation of the present invention is any one in the modes that those skilled in the art were familiar with such as vacuum filtration, centrifuging, filter press, spinning.Described drying is any one or its combination in the modes that those skilled in the art were familiar with such as vacuum-drying, air blast heated drying, microwave drying.
Cellulase preparation of the present invention is any one in acidic cellulase or the mixture that comprises acidic cellulase, beta-glucosidase.The addition of described cellulase preparation is acidic cellulase 10～40FPU/g bagasse, beta-glucosidase 5～20CBIU/g bagasse.Described enzymolysis time is 24～72 hours.Described 0.2mol/L acetic acid-sodium-acetate buffer pH is 4.5～5.2, by the general knowledge preparation of this area.For example 0.2mol/L, pH5.2:0.2mol/L sodium acetate soln 7.90 (L) mix with 0.2mol/L acetum 2.10 (L).0.2mol/L, pH4.8: on 0.2mol/L, pH5.2 damping fluid basis, add the 0.2mol/L acetum and regulate pH to 4.8.Other by that analogy.
Hydrolysis of the present invention, extraction process do not have particular requirement or restriction to equipment, can in the reaction kettle of broad variety, specification, carry out.How those skilled in the art carry out the fermentation of ethanol, butanols or Xylitol and the separation and Extraction purifying of D-wood sugar after knowing acquisition hydrolyzed solution and enzymolysis solution.
Below in conjunction with embodiment the present invention is described further.But protection scope of the present invention can not be thought and only is confined to following embodiment.Do not breaking away under the prerequisite that the present invention conceives basically, simple deduction that the those skilled in the art makes in view of the above or equal alternative all belong to protection scope of the present invention.
Embodiment 1
The method of the said a kind of lignocellulose comprehensive utilization of resources coproduction xylogen of present embodiment mainly may further comprise the steps:
(1) bagasse is removed granule foreign, foreign matters such as stone, mechanical disintegration to 1～5mm size;
(2) ultra diluted acid catalysis pyrohydrolysis: take by weighing dried pulp 1000g, adding concentration at 1: 10 by solid-to-liquid ratio (W/W) is diluted acid (aqueous nitric acid) solution of 0.5wt%, soaks 10min under the room temperature and is placed in the autoclave hydrolysis 10min under 145 ℃ of conditions; Cooling rapidly after hydrolysis is accomplished, solid-liquid separation gets hydrolytic residue and hydrolyzed solution;
(3) washing: the hydrolytic residue of step (2) is added entry by solid-to-liquid ratio (W/W) at 1: 20, wash wherein solubility hydrolyzate, solid-liquid separation, washing times is 2 times, gets washings and washing hydrolytic residue; The hydrolyzed solution of washings and step (2) merges, and the semicellulose recovery (in wood sugar) is 71%; It can be used for separation and purification and prepares the D-wood sugar, also can be used for the fermentative prodn of products such as ethanol, butanols, Xylitol, also can further produce chemical such as furfural, furans, levulinic acid through chemical conversion;
(4) NH
3Aqueous systems extracting: the hydrolytic residue of thorough washing in the step (3) is pressed solid-to-liquid ratio (W/W) 1: 8 and 10wt%NH
3Aqueous systems is mixed, and places autoclave, and in 130 ℃ of stirring extracting 90min, solid-liquid separation after the reduction temperature gets extracting residue and extract, the Mierocrystalline cellulose recovery 83%; The main cellulose component of extracting residue (still containing a small amount of semicellulose and xylogen) can be used for the fermentative prodn of ethanol, butanols, sorbyl alcohol, succsinic acid etc. through enzymic hydrolysis for C6 sugar; Extract gets into next step processing;
(5) NH
3Stripping reclaim: the extract of heat is that carrier remove NH with the air in 60 ℃ in stripping tower in the step (4)
3, extract pH value is controlled at 11.0-12.5 in the stripping process, the NH of stripping
3Through the absorption tower with water absorb ammoniacal liquor, can be back to NH
3Reuse in the aqueous systems extraction steps;
(6) lignin separation preparation: NH in the step (5)
3After the remaining extract cooling after stripping reclaims, add 10% sulfuric acid and regulate pH=3.0, make the xylogen deposition separate out, behind solid-liquid separation, 80 ℃ of air blast heated dryings, obtain lignin product 149g, yield 14.9%, the recovery 71%.
(7) enzymic hydrolysis: the 0.2mol/L acetic acid-sodium-acetate buffer that in filtering the extracting residue 466g (dry weight) that collects, adds 5359g pH=4.5; Make that extracting residue final concentration is 8wt%; Add cellulase preparation simultaneously; Described cellulase preparation comprises acidic cellulase and beta-glucosidase, and wherein the acidic cellulase addition is 115mL (enzyme liquid vigor 120FPU/mL; Adding proportion 30FPU/g residue), the beta-glucosidase addition is 46mL (enzyme liquid vigor 100CBIU/mL; Adding proportion 10CBIU/g residue), stir in 46 ℃ of constant temperature, enzymolysis 72 hours obtains saccharification liquid, and concentration of reduced sugar is 64.8g/L, and the cellulase hydrolysis rate reaches 91%.
Embodiment 2
The method of the said a kind of lignocellulose comprehensive utilization of resources coproduction xylogen of present embodiment mainly may further comprise the steps:
(1) the sugarcane leaf is removed granule foreign, foreign matters such as stone, mechanical disintegration to 1～5mm size;
(2) ultra diluted acid catalysis pyrohydrolysis: take by weighing dried sugarcane leaf 1000g, adding concentration at 1: 40 by solid-to-liquid ratio (W/W) is the dilute acid solution (aqueous sulfuric acid) of 0.05wt%, soaks 60min under the room temperature and is placed in the autoclave hydrolysis 2min under 180 ℃ of conditions; Cooling rapidly after hydrolysis is accomplished, solid-liquid separation gets hydrolytic residue and hydrolyzed solution;
(3) washing: the hydrolytic residue of step (2) is added entry by solid-to-liquid ratio (W/W) at 1: 10, wash wherein solubility hydrolyzate, solid-liquid separation, washing times is 4 times; The hydrolyzed solution of washings and step (2) merges, and the semicellulose recovery (in wood sugar) is 77%; It can be used for separation and purification and prepares the D-wood sugar, also can be used for the fermentative prodn of products such as ethanol, butanols, Xylitol, also can further produce chemical such as furfural, furans, levulinic acid through chemical conversion;
(4) NH
3Aqueous systems extracting: the hydrolytic residue of thorough washing in the step (3) is pressed solid-to-liquid ratio (W/W) 1: 25 and 1wt%NH
3Aqueous systems is mixed, and places autoclave, and in 190 ℃ of stirring extracting 15min, solid-liquid separation after the reduction temperature gets extracting residue and extract, the Mierocrystalline cellulose recovery 85%; The main cellulose component of extracting residue (still containing a small amount of semicellulose and xylogen) can be used for the fermentative prodn of ethanol, butanols, sorbyl alcohol, succsinic acid etc. through enzymic hydrolysis for C6 sugar; Extract gets into next step processing;
(5) NH
3Stripping reclaim: the extract of heat is that carrier remove NH with the air in 45 ℃ in stripping tower in the step (4)
3, extract pH value is controlled at 11.5～12.0 in the stripping process, the NH of stripping
3Absorb to such an extent that ammoniacal liquor reuses through the absorption tower with water;
(6) lignin separation preparation: NH in the step (5)
3After the remaining extract cooling after stripping reclaims, add 10% sulfuric acid and regulate pH=5.0, make the xylogen deposition separate out, after solid-liquid separation, vacuum-drying, obtain lignin product 135g, yield 13.5%, the recovery 73%.
(7) enzymic hydrolysis: the 0.2mol/L acetic acid-sodium-acetate buffer that in filtering the extracting residue 491g (dry weight) that collects, adds 24010g pH=5.2; Make that extracting residue final concentration is 2wt%; Add cellulase preparation simultaneously; Described cellulase preparation comprises acidic cellulase and beta-glucosidase, and wherein the acidic cellulase addition is 163.5mL (enzyme liquid vigor 120FPU/mL; Adding proportion 40FPU/g residue), the beta-glucosidase addition is 98mL (enzyme liquid vigor 100CBIU/mL; Adding proportion 20CBIU/g residue), stir in 50 ℃ of constant temperature, enzymolysis 24 hours obtains saccharification liquid, and concentration of reduced sugar is 15.4g/L, and the cellulase hydrolysis rate reaches 90%.
Embodiment 3
The method of the said a kind of lignocellulose comprehensive utilization of resources coproduction xylogen of present embodiment mainly may further comprise the steps:
(1) stalk is removed granule foreign, foreign matters such as stone, mechanical disintegration to 1～5mm size;
(2) ultra diluted acid catalysis pyrohydrolysis: take by weighing dry straw 1000g, adding concentration at 1: 20 by solid-to-liquid ratio (W/W) is diluted acid (sulfuric acid) aqueous solution of 0.3wt%, soaks 40min under the room temperature and is placed in the autoclave hydrolysis 5min under 170 ℃ of conditions; Cooling rapidly after hydrolysis is accomplished, solid-liquid separation gets hydrolytic residue and hydrolyzed solution;
(3) washing: the hydrolytic residue of step (2) is added entry by solid-to-liquid ratio (W/W) at 1: 15, wash wherein solubility hydrolyzate, solid-liquid separation, washing times is 3 times; The hydrolyzed solution of washings and step (2) merges, and the semicellulose recovery (in wood sugar) is 77%; It can be used for separation and purification and prepares the D-wood sugar, also can be used for the fermentative prodn of products such as ethanol, butanols, Xylitol, also can further produce chemical such as furfural, furans, levulinic acid through chemical conversion;
(4) NH
3Aqueous systems extracting: the hydrolytic residue of thorough washing in the step (3) is pressed solid-to-liquid ratio (W/W) 1: 20 and 6wt%NH
3Aqueous systems is mixed, and places autoclave, and in 185 ℃ of stirring extracting 30min, solid-liquid separation after the reduction temperature gets extracting residue and extract, the Mierocrystalline cellulose recovery 90%; The main cellulose component of extracting residue (still containing a small amount of semicellulose and xylogen) can be used for the fermentative prodn of ethanol, butanols, sorbyl alcohol, succsinic acid etc. through enzymic hydrolysis for C6 sugar; Extract gets into next step processing;
(5) NH
3Stripping reclaim: the extract of heat is that carrier remove NH with the air in 50 ℃ in stripping tower in the step (4)
3, extract pH value is controlled at 11.5～12.5 in the stripping process, the NH of stripping
3Absorb to such an extent that ammoniacal liquor reuses through the absorption tower with water;
(6) lignin separation preparation: NH in the step (5)
3After the remaining extract cooling after stripping reclaims, add 10% sulfuric acid and regulate pH=4.0, make the xylogen deposition separate out, after solid-liquid separation, vacuum-drying, obtain lignin product 145g, yield 14.5%, the recovery 75%.
(7) enzymic hydrolysis: in filtering 0.2mol/L acetic acid-sodium-acetate buffer that the extracting residue 483g (dry weight) that collects adds 7567g pH=4.8; Make that extracting residue final concentration is 6wt%; Add cellulase preparation simultaneously, wherein the acidic cellulase addition is 41mL (enzyme liquid vigor 120FPU/mL; Adding proportion 10FPU/g residue), the beta-glucosidase addition is 25mL (enzyme liquid vigor 100CBIU/mL; Adding proportion 5CBIU/g residue), stirred enzymolysis 60 hours in 48 ℃, obtain saccharification liquid, concentration of reduced sugar is 49.1g/L, and the cellulase hydrolysis rate is 94%.
Embodiment 4
The method of the said a kind of lignocellulose comprehensive utilization of resources coproduction xylogen of present embodiment mainly may further comprise the steps:
(1) corn cob is removed granule foreign, foreign matters such as stone, mechanical disintegration to 1～5mm size;
(2) ultra diluted acid catalysis pyrohydrolysis: take by weighing dried corn cob 1000g; Adding concentration at 1: 30 by solid-to-liquid ratio (W/W) is the diluted acid (mixed solution of sulfuric acid and hydrochloric acid of 0.1wt%; Both have 1: 1) solution, soak 30min and be placed in the autoclave hydrolysis 6min under 160 ℃ of conditions under the room temperature; Cooling rapidly after hydrolysis is accomplished, solid-liquid separation gets hydrolytic residue and hydrolyzed solution;
(3) washing: the hydrolytic residue of step (2) is added entry by solid-to-liquid ratio (W/W) at 1: 15, wash wherein solubility hydrolyzate, solid-liquid separation, washing times is 3 times; The hydrolyzed solution of washings and step (2) merges, and the semicellulose recovery (in wood sugar) is 74%; It can be used for separation and purification and prepares the D-wood sugar, also can be used for the fermentative prodn of products such as ethanol, butanols, Xylitol, also can further produce chemical such as furfural, furans, levulinic acid through chemical conversion;
(4) NH
3Aqueous systems extracting: the hydrolytic residue of thorough washing in the step (3) is pressed solid-to-liquid ratio (W/W) 1: 16 and 3wt%NH
3Aqueous systems is mixed, and places autoclave, and in 150 ℃ of stirring extracting 45min, solid-liquid separation after the reduction temperature gets extracting residue and extract, the Mierocrystalline cellulose recovery 88%; The main cellulose component of extracting residue (still containing a small amount of semicellulose and xylogen) can be used for the fermentative prodn of ethanol, butanols, sorbyl alcohol, succsinic acid etc. through enzymic hydrolysis for C6 sugar; Extract gets into next step processing;
(5) NH
3Stripping reclaim: the extract of heat is that carrier remove NH with the air in 55 ℃ in stripping tower in the step (4)
3, extract pH value is controlled at 11.5～12.0 in the stripping process, the NH of stripping
3Absorb to such an extent that ammoniacal liquor reuses through the absorption tower with water;
(6) lignin separation preparation: NH in the step (5)
3After the remaining extract cooling after stripping reclaims, add 10% sulfuric acid and regulate pH=3.0～5.0, make the xylogen deposition separate out, after solid-liquid separation, vacuum-drying, obtain lignin product 131g, yield 13.1%, the recovery 71%;
(7) enzymic hydrolysis: in filtering 0.2mol/L acetic acid-sodium-acetate buffer that the extracting residue 552g (dry weight) that collects adds 10488g pH=4.7; Make that extracting residue final concentration is 5wt%; Add cellulase preparation simultaneously, wherein the acidic cellulase addition is 92mL (enzyme liquid vigor 120FPU/mL; Adding proportion 20FPU/g extracting residue), the beta-glucosidase addition is 55mL (enzyme liquid vigor 100CBIU/mL; Adding proportion 10CBIU/g extracting residue), stirred enzymolysis 48 hours in 49 ℃, obtain saccharification liquid, concentration of reduced sugar is 41.9g/L, and the cellulase hydrolysis rate is 94%.
Embodiment 5
The method of the said a kind of lignocellulose comprehensive utilization of resources coproduction xylogen of present embodiment mainly may further comprise the steps:
(1) cornstalk is removed granule foreign, foreign matters such as stone, mechanical disintegration to 1～5mm size;
(2) ultra diluted acid catalysis pyrohydrolysis: take by weighing dried cornstalk 1000g; Adding concentration at 1: 40 by solid-to-liquid ratio (W/W) is diluted acid (hydrochloric acid and the phosphoric acid of 0.08wt%; 1: 1) aqueous solution, soak 60min and be placed in the autoclave hydrolysis 3min under 180 ℃ of conditions under the room temperature; Cooling rapidly after hydrolysis is accomplished, solid-liquid separation gets hydrolytic residue and hydrolyzed solution;
(3) washing: the hydrolytic residue of step (2) is added entry by solid-to-liquid ratio (W/W) at 1: 10, wash wherein solubility hydrolyzate, solid-liquid separation, washing times is 4 times; The hydrolyzed solution of washings and step (2) merges, and the semicellulose recovery (in wood sugar) is 81%; It can be used for separation and purification and prepares the D-wood sugar, also can be used for the fermentative prodn of products such as ethanol, butanols, Xylitol, also can further produce chemical such as furfural, furans, levulinic acid through chemical conversion;
(4) NH
3Aqueous systems extracting: the hydrolytic residue of thorough washing in the step (3) is pressed solid-to-liquid ratio (W/W) 1: 20 and 7wt%NH
3Aqueous systems is mixed, and places autoclave, and in 140 ℃ of stirring extracting 55min, solid-liquid separation after the reduction temperature gets extracting residue and extract, the Mierocrystalline cellulose recovery 84%; The main cellulose component of extracting residue (still containing a small amount of semicellulose and xylogen) can be used for the fermentative prodn of ethanol, butanols, sorbyl alcohol, succsinic acid etc. through enzymic hydrolysis for C6 sugar; Extract gets into next step processing;
(5) NH
3Stripping reclaim: the extract of heat is that carrier remove NH with the air in 60 ℃ in stripping tower in the step (4)
3, extract pH value is controlled at 11.5～12.0 in the stripping process, the NH of stripping
3Absorb to such an extent that ammoniacal liquor reuses through the absorption tower with water;
(6) lignin separation preparation: NH in the step (5)
3After the remaining extract cooling after stripping reclaims, add 10% sulfuric acid and regulate pH=3.5, make the xylogen deposition separate out, after solid-liquid separation, vacuum-drying, obtain lignin product 147g, yield 14.7%, the recovery 73%;
(7) enzymic hydrolysis: in step (4), filter the 0.2mol/L acetic acid-sodium-acetate buffer that adds 12480gpH 5.0 among the extracting residue 520g (dry weight) that collects; Make that extracting residue final concentration is 4wt%; Add cellulase preparation simultaneously, wherein the acidic cellulase addition is 171mL (enzyme liquid vigor 120FPU/mL; Adding proportion 20FPU/g extracting residue), the beta-glucosidase addition is 82mL (enzyme liquid vigor 100CBIU/mL; Adding proportion 8CBIU/g extracting residue), stirred enzymolysis 36 hours in 50 ℃, obtain saccharification liquid, concentration of reduced sugar is 33.8g/L, and the cellulase hydrolysis rate is 92%.
More than be merely specific embodiment of the present invention, do not limit protection scope of the present invention with this; Any replacement and the improvement on the basis of not violating the present invention's design, done all belong to protection scope of the present invention.
Claims (9)
1. the method for a lignocellulose comprehensive utilization of resources coproduction xylogen is characterized in that, may further comprise the steps:
(1) lignocellulosic material is carried out removal of impurities, pulverization process;
(2) ultra diluted acid catalysis pyrohydrolysis: lignocellulosic material is that 1: 10～40 adding concentration are 0.05%～0.5% inorganic acid aqueous solution by solid-to-liquid ratio W/W; Soaking at room temperature 10～60min is placed in the autoclave, hydrolysis 2～10min under 145 ℃～180 ℃ conditions; Cooling rapidly after hydrolysis is accomplished, solid-liquid separation gets hydrolytic residue and hydrolyzed solution;
(3) washing: is 1: 10～20 to add entry with the hydrolytic residue of step (2) by solid-to-liquid ratio W/W, and repetitive scrubbing is the solubility hydrolyzate wherein, and washing times is 2～4 times, solid-liquid separation, washings and washing hydrolytic residue;
(4) NH
3The aqueous systems extracting: is 1: 8～25 and NH with the washing hydrolytic residue in the step (3) by solid-to-liquid ratio W/W
3Aqueous systems is mixed, and places autoclave, and in 130 ℃～190 ℃ stirring extracting 15～90min, temperature reduces the back solid-liquid separation, gets extracting residue and extract, wherein, and NH
3NH in the aqueous systems
3Concentration is 1wt%～10wt%;
(5) NH
3Stripping reclaim: in the step (4) extract of heat in 45 ℃～60 ℃ in stripping tower gas expose to the sun and remove NH
3
(6) lignin separation preparation: stripping reclaims NH in step (5)
3After remaining extract in add sulfuric acid and regulate pH=3.0～5.0, make the xylogen deposition separate out, after solid-liquid separation, drying, obtain lignin product.
2. the method for lignocellulose comprehensive utilization of resources coproduction xylogen according to claim 1; It is characterized in that; Also comprise the enzymic hydrolysis of extracting residue: in the extracting residue of step (4), add an amount of 0.2mol/L acetic acid-sodium-acetate buffer, make that extracting residue final concentration is 2wt%～8wt%, adds cellulase preparation simultaneously; Constant temperature stirring, enzymolysis promptly obtain saccharification liquid under 46 ℃～50 ℃ conditions.
3. the method for lignocellulose comprehensive utilization of resources coproduction xylogen according to claim 1 is characterized in that, the inorganic acid aqueous solution described in the step (2) is a kind of or its mixing in sulfuric acid, hydrochloric acid, nitric acid and the phosphate aqueous solution.
4. the method for lignocellulose comprehensive utilization of resources coproduction xylogen according to claim 3 is characterized in that said inorganic acid aqueous solution is an aqueous sulfuric acid.
5. the method for lignocellulose comprehensive utilization of resources coproduction xylogen according to claim 1 is characterized in that, the NH described in the step (4)
3NH in the aqueous systems
3Concentration is 2wt%～8wt%.
6. according to the method for each described lignocellulose comprehensive utilization of resources coproduction xylogen of claim 1-5, it is characterized in that the stripping tower described in the step (5) removes NH
3Process in extract pH value control 11.5～12.0.
7. the method for lignocellulose comprehensive utilization of resources coproduction xylogen according to claim 2 is characterized in that, described cellulase preparation is acidic cellulase or the mixture that comprises acidic cellulase, beta-glucosidase.
8. the method for lignocellulose comprehensive utilization of resources coproduction xylogen according to claim 7 is characterized in that, the consumption of acidic cellulase is 10～40FPU/g extracting residue, and the consumption of beta-glucosidase is 5～20CBIU/g extracting residue.
9. according to the method for claim 2 or 7 described lignocellulose comprehensive utilization of resources coproduction xylogen, it is characterized in that described enzymolysis time is 24～72 hours; Described 0.2mol/L acetic acid-sodium-acetate buffer pH is 4.5～5.2.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103773815A (en) * | 2014-01-29 | 2014-05-07 | 中国石油集团东北炼化工程有限公司吉林设计院 | Pretreatment method of lignocellulose |
| CN105039458A (en) * | 2015-07-28 | 2015-11-11 | 天津科技大学 | Method for realizing clean separation of carbohydrate from lignin components in corncob residue |
| CN108586771A (en) * | 2018-03-30 | 2018-09-28 | 中国林业科学研究院 | A method of efficiently separating lignin in wood cell wall |
| CN109957982A (en) * | 2019-04-24 | 2019-07-02 | 吴学军 | A kind of procedural blast pulping method of agricultural crop straw |
| CN111995768A (en) * | 2020-09-01 | 2020-11-27 | 高维阳 | Method for extracting wood fiber from branch straw |
| CN112458132A (en) * | 2020-11-17 | 2021-03-09 | 汕头大学 | Method for preparing multi-element antibacterial probiotic by using single raw material |
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| CN101130793A (en) * | 2007-08-20 | 2008-02-27 | 吉林大学 | Novel method for producing fuel alcohol by rice hull and comprehensive utilization of resource |
| JP2009284867A (en) * | 2008-05-30 | 2009-12-10 | Toshiba Corp | Cellulose saccharification system, ethanol production system and method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101130793A (en) * | 2007-08-20 | 2008-02-27 | 吉林大学 | Novel method for producing fuel alcohol by rice hull and comprehensive utilization of resource |
| JP2009284867A (en) * | 2008-05-30 | 2009-12-10 | Toshiba Corp | Cellulose saccharification system, ethanol production system and method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103773815A (en) * | 2014-01-29 | 2014-05-07 | 中国石油集团东北炼化工程有限公司吉林设计院 | Pretreatment method of lignocellulose |
| CN105039458A (en) * | 2015-07-28 | 2015-11-11 | 天津科技大学 | Method for realizing clean separation of carbohydrate from lignin components in corncob residue |
| CN108586771A (en) * | 2018-03-30 | 2018-09-28 | 中国林业科学研究院 | A method of efficiently separating lignin in wood cell wall |
| CN109957982A (en) * | 2019-04-24 | 2019-07-02 | 吴学军 | A kind of procedural blast pulping method of agricultural crop straw |
| CN109957982B (en) * | 2019-04-24 | 2020-11-17 | 吴学军 | Programmed explosion pulping method for crop straws |
| CN111995768A (en) * | 2020-09-01 | 2020-11-27 | 高维阳 | Method for extracting wood fiber from branch straw |
| CN112458132A (en) * | 2020-11-17 | 2021-03-09 | 汕头大学 | Method for preparing multi-element antibacterial probiotic by using single raw material |
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