CN103030815A - Comprehensive utilization technology of biomass raw materials - Google Patents
Comprehensive utilization technology of biomass raw materials Download PDFInfo
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Abstract
The invention relates to a method of comprehensively utilizing biomass raw materials, in particular to a method of comprehensively utilizing cellulose, hemicellulose and lignin in the biomass raw materials. The method comprises the steps that mixed organic acid of formic acid and acetic acid is utilized to boil the biomass raw materials by the catalytic action of hydrogen peroxide; and cellulose, lignin and hemicellulose are extracted respectively. The obtained cellulose is high in purity and can be used in the textile industry; and the comprehensive and stable proceeding of three routes improves extraction rates of the three products.
Description
Technical field
The present invention relates to a kind of method that fully utilizes biomass material, specifically a kind of method of extracting Mierocrystalline cellulose in the biomass material, hemicellulose and xylogen and further co-producing bio carbon.
Background technology
Biomass material exists with the form of plant materials, main component is Mierocrystalline cellulose, hemicellulose and xylogen, wherein, Mierocrystalline cellulose accounts for about 40%, hemicellulose accounts for about 25%, xylogen accounts for about 20%, and the annual biomass material total amount that is generated by photosynthesis surpasses 2,000 hundred million tons on the earth, so biomass material is renewable resources abundant, the most cheap on the earth.
Mierocrystalline cellulose is the main component of plant cell wall.The whole world is used for the Mierocrystalline cellulose of weaving papermaking, reaches 8,000,000 tons every year.In addition, Mierocrystalline cellulose with separation and purification is done raw material, can make artificial silk, the ether derivatives such as the ester derivative such as cellulose film and nitric ether, acetic ester and methylcellulose gum, ethyl cellulose, Xylo-Mucine are used for the aspects such as petroleum drilling, food, ceramic glaze, daily use chemicals, synthesis of detergent, graphite product, pencil manufacturing, battery, coating, building materials, decoration, mosquito-repellent incense, tobacco, papermaking, rubber, agricultural, tackiness agent, plastics, explosive, electrician and Scientific Research Equipments.
At occurring in nature, the reserves of xylogen are only second to Mierocrystalline cellulose, and all regenerate with 50,000,000,000 tons speed every year.Pulp and paper industry will be isolated about 1.4 hundred million tons of Mierocrystalline celluloses every year from plant, obtain simultaneously the xylogen byproduct about 5,000 ten thousand tons, but up to now, surpass 95% xylogen still with " black liquor " directly enter rivers or concentrated after burn, seldom be utilized effectively.
In fact, xylogen is a kind of of great value industrial chemicals, highly purified sulphur-free lignin can be used as the polymeric additive such as phenolic resin, polyurethane foam, Resins, epoxy and soil improvement agent, pesticide slow-releasing agent etc., and lignin is used the added value that can make its added value in these areas far above reclaiming heat after the burning that acts as a fuel.At present, lignin is mainly as the pulping and paper-making co-production, such as Sulfite lignin, kraft lignin etc.But these lignins contain element sulphur simultaneously lower, the complicated component of lignin purity, molecular weight distribution is wide, viscosity is low, dispersity is high, poor processability, almost do not have a thermoplastic property, thereby has greatly limited its industrial application.
Furfural, have another name called furtural, it is by two on the furan nucleus two keys and an aldehyde radical, the chemical structure of this uniqueness, can make it that reactions such as oxidation, hydrogenation, chlorination, nitrated and condensation occur, and then generate a lot of Chemicals, so be widely used in a plurality of production fields such as agricultural chemicals, medicine, petrochemical industry, foodstuff additive and casting.Furfural is the vegetable fibre that is rich in piperylene, is raw material production such as corn cob, maize straw, straw, bagasse, cotton seed hulls, straw etc., and its principle is that piperylene at first is hydrolyzed into pentose in the vegetable fibre, and then the pentose dehydration generates furfural.
The producing and manufacturing technique of furfural mainly contains single stage method and two step method in the world.Single stage method is that pentosan hydralysis and two reactions of pentose dehydration generation furfural are once finished in same reactor; The main drawback that single stage method exists is that steam consumption is large, and furaldehyde yield is low, produces a large amount of liquid and waste slag produced etc.Two-step approach is that the process that pentosan hydralysis in the raw material and pentose dehydration generate furfural is to carry out at least two different reactors.Than single stage method, two step method has overcome the difficult problems such as existing furfural production feed stock conversion is low, the generation processing wastewater is difficult to administer, the furfural dregs utility value is low.Along with the development of furfurol industry, and the raising of raw material requirements of comprehensive utilization, development two-step approach production technique, the Mierocrystalline cellulose in the separate raw materials and hemicellulose also are used respectively, are the inevitable development trend of furfurol industry.
At present, mainly be to use boiling to propose hemicellulose, generate the required target products such as ethanol by cellulase again by alkaline hydrolysis proposition xylogen, last Mierocrystalline cellulose to the extraction of three kinds of main components in the biomass material.But whole processing step is loaded down with trivial details, during this time will be through the Decomposition of boiling and alkaline hydrolysis, the required product of loss that also can be to a certain degree, therefore select suitable technique under the prerequisite of not destroying Mierocrystalline cellulose, hemicellulose and xylogen vigor, to greatest extent the three is separated and extract the maximum focus that has become this technical study.
Chinese patent CN101864683A discloses a kind of pretreatment process of lignocellulose raw material, this patent with the xylogen raw material with after the mixed solution of organic acid soln and catalyzer mixes, carry out the first step and process, obtain liquid-solid mixture and carry out solid-liquid separation, obtain pretreatment fluid and cellulose solids; Adopt the organic acid soln washing to obtain cellulose solids; The pre-treatment black liquor that obtains be cycled to used in the first step treating processes after the washing black liquid that obtains is mixed; The mixing black liquor that then will recycle at least 3 times carries out organic acid, lignin products and syrup solution recovery.The black liquor of collecting is carried out flash distillation or evaporation, obtain organic acid and concentrated black liquor, the water that adds 2-10 times of volume in the black liquor obtains lignin products and syrup solution, and the organic acid that reclaims then refluxes and processes for the first step, thereby realizes the higher value application of lignocellulose raw material.But also there is following shortcoming in this patent: 1, the description from specification sheets can be found out, this technique is to adopt organic acid and the catalyst mix take sulfuric acid as representative to carry out the first step catalysis, need to add sulfuric acid in the reaction process and carry out catalysis, inevitably make sulfur-bearing in the follow-up xylogen that obtains; 2, the common boiling biomass of this process using organic acid and the catalyzer take sulfuric acid as representative, in distillation organic acid step, if the organic acid distillation not exclusively, then xylogen can't be separated out fully, if after organic acid distilled out fully, the sulfuric acid concentration that then adds wherein rises, and meeting affects the extraction yield of xylogen so that xylogen charing wherein; Although extract in the 3 whole techniques and all use identical organic acid with the washing the fibre element, and pretreatment fluid and the washings collected are directly used in the reactor that is circulated to the first step, but also gathered in a large number dissolving xylogen and pentose solution wherein in the whole mixed solution, saturation ratio restriction in view of the organic acid extraction, its degree of functioning of mixing the black liquid extraction xylogen can significantly reduce, therefore, although this step is circulating reaction, also little for the extraction efficiency effect of integral body; 4, in the pretreatment fluid of collecting and the washings owing to be dissolved with the pentose that a large amount of hemicellulose boilings generate, and pentose repeatedly can constantly contact with organic acid in the working cycle along with mixed solution, esterification occurs generate the ester class, this patent is that comprehensive utilization take biomass material is as purpose, therefore whether can obtain separately pentose for whole piece technique and pay no attention to, but for obtaining pentose take separation for the technique of purpose, this technique is also inapplicable; 5, the black liquor that is mixed to get need to circulate and carry out evaporation process more than 3 times to isolate organic acid again, and the concentrated solution that obtains of dilution so that xylogen separate out, meeting is so that the quantity of the black liquor of disposable processing and concentrated solution is very big, not only affects processing efficiency but also is difficult to realize the continuity of technique; Can find out from specification sheets that 6, only for 38-55%, lignin extraction rate are 6-16%, the extraction yield of whole technique is relatively low for cellulosic extraction yield in this technique; The Mierocrystalline cellulose purity that adopts this technique to extract is low, can not satisfy textile applications.
Chinese patent CN1170031C discloses a kind of method of producing paper pulp with the mixture of formic acid and acetic acid as cooking chemical.This patent is when producing paper pulp with formic acid boiling herbaceous plant and deciduous tree, add acetic acid as additional cooking chemical, can obtain containing hemicellulose and cellulosic paper pulp, and the mix acid liquor that used cooking liquor distills out formic acid and acetic acid carries out recycle.Although the method has solved the problem that needs to add catalyzer in the process of boiling biomass, but because the method is mainly for the preparation of paper pulp, its objective is the hemicellulose that keeps to greatest extent Mierocrystalline cellulose and part, its whole technological design all is with this end in view, and whether do not pay attention to for the loss of xylogen and pentose wherein, although therefore this technique is with Mierocrystalline cellulose extraction and application from biomass material, but can not realize Mierocrystalline cellulose, separating of xylogen and hemicellulose, and adopt in the paper pulp that this technique obtains Mierocrystalline cellulose purity low, papermaking can only be used for, higher industrial requirements can not be satisfied.
Chinese patent CN101514349A discloses a kind of method that is prepared alcohol fuel by bamboo fiber.This patent also is the mix acid liquor boiling hydrolyzed hemicellulose with formic acid and acetic acid, and directly adds elutriation in the filtrate of deviating from and go out the xylogen precipitation and isolate xylogen with this and be used.Although this patent in a technique circuit with Mierocrystalline cellulose, hemicellulose and xylogen are separated, the design of this technique is also to extract Mierocrystalline cellulose as final purpose, the loss of xylogen and pentose is not considered in the design of whole piece technique, it is in the step of separating lignin extracting in water precipitation in one step, understand because containing in a large number formic acid and acetic acid in the solution so that xylogen is difficult to all deviate from, also can can't guarantee that wherein xylogen separates out fully because of the dissolving of formic acid and acetic acid even if add in a large number water, cause the xylogen loss, obviously, this technique only emphasis has considered to extract to greatest extent cellulosic technique, extracts highly purified Mierocrystalline cellulose for three kinds of materials of comprehensive extraction and there is no directive function.
Summary of the invention
For this reason, technical problem to be solved by this invention is the integrated extraction technique route of biomass material in the prior art, each problem that the component yield is low, purity is low that obtains, so provide a kind of by rational parameter adjustment can the high efficiency separation lignin, the comprehensive utilization process of Mierocrystalline cellulose and half fiber;
For solving the problems of the technologies described above, the comprehensive utilization process of biomass material of the present invention comprises the steps:
(1) with after the biomass material pulverizing, under the katalysis of hydrogen peroxide, use is carried out boiling by the organic acid solution that formic acid, acetic acid form to described raw material, 80-145 ℃ of control boiling temperature, the solid-liquid mass ratio is 1:5-1:25, reaction times 10-60min, and the reaction solution that obtains carried out the solid-liquid separation first time; In the described organic acid solution, total acid is dense to be 60-95%, and the mass ratio of described acetic acid and formic acid is 1:1-1:15, and surplus is water; Hydrogen peroxide accounts for the 1-8% of biomass material;
(2) collect the solid that the described first time, solid-liquid separation obtained, under the katalysis of hydrogen peroxide, the mix acid liquor that adopts formic acid, acetic acid to form carries out pickling to described solid, 20-60 ℃ of control pickling temperature, the solid-liquid mass ratio is 1:4-1:20, and the reaction solution that obtains is carried out the solid-liquid separation second time; Hydrogen peroxide accounts for the 1-3% of biomass material, and the total acid of described mix acid liquor is dense to be 75-95%, and the mass ratio of acetic acid and formic acid is 1:1-1:15;
(3) collect the solid that the described second time, solid-liquid separation obtained, and wash, the control washing temperature is 60-90 ℃, and starching dense is 1-10%, and the washing slurry that obtains is carried out for the third time solid-liquid separation;
(4) collect solid and the screening that described for the third time solid-liquid separation obtains and obtain the screened stock Mierocrystalline cellulose, described screened stock Mierocrystalline cellulose obtains required Mierocrystalline cellulose after bleaching;
(5) collect step for the first time and the liquid that obtains of solid-liquid separation for the second time, at 110-160 ℃, evaporate under the 301-701kpa and obtain formic acid and acetic acid steam and concentrated solution, the solids content of described concentrated solution is 60wt%-90wt%;
(6) concentrated solution with gained in the step (5) adds organic solvent, stirs, and carries out solid-liquid separation the 4th time, and wherein, the adding quality of described organic solvent is 1-10 times of described concentrated solution quality;
(7) collect the solid thin up that obtains after the 4th solid-liquid separation and stir, and the solid that carries out obtaining after the 5th solid-liquid separation is required xylogen through washing;
(8) after described the 5th solid-liquid separation, after the liquid process dehydration carburizing reagent that obtains, carry out solid-liquid separation the 6th time, the solid that obtains is biological carbon, and the further rectifying of the liquid that obtains obtains the finished product furfural.
In the comprehensive utilization process of biomass material, described dehydration carburizing reagent, the control temperature of reaction is 170-220 ℃, reaction times 90-300min, and adding the acid saline catalyst, the consumption of described acid saline catalyst is the 0.05wt%-0.5wt% of the 5th liquid mass that solid-liquid separation obtains.
In the comprehensive utilization process of biomass material, described dehydration carburizing reagent, the control temperature of reaction is 170-190 ℃, reaction times 90-180min.
In the comprehensive utilization process of biomass material, described acid saline catalyst is hydrosulfate, supercarbonate, hydrophosphate and dihydrogen phosphate.。
In the comprehensive utilization process of biomass material, described bleaching comprises: alkaline purification, and described alkali consumption accounts for the 1-6% of described screened stock Mierocrystalline cellulose quality, and temperature is 50-100 ℃, and extracting time 0.5-4h starches dense 5-15%; Sequestrant pre-treatment, the quality of described sequestrant account for the 0.1-3% of described screened stock Mierocrystalline cellulose quality, and the pH value is controlled between the 2-4, and temperature 50-80 ℃, time 0.5-2h starches dense 4-7%; Alkaline hydrogen peroxide bleaching, the quality of alkaline hydrogen peroxide account for the 3-6% of described screened stock Mierocrystalline cellulose quality, and the pH value is controlled between the 10-12, and temperature 70-120 ℃, bleaching time 1-6h starches dense 5-20%; And acid treatment, the quality of described acid accounts for the 1%-6% of described screened stock Mierocrystalline cellulose quality, and the pH value is controlled between the 2-4, and temperature 20-45 ℃, time 0.5-3h starches dense 3-6%.
Preferably, in the step of described alkaline purification, described alkali consumption accounts for the 2-5% of described screened stock Mierocrystalline cellulose quality, and temperature is 85-95 ℃, and extracting time 1-3h starches dense 6-12%; The alkali reagent that described alkaline purification process is selected is sodium hydroxide and/or potassium hydroxide; State in the pretreated step of sequestrant, the quality of described sequestrant accounts for the 0.1-0.5% of described screened stock Mierocrystalline cellulose quality, temperature 50-65 ℃, time 1.5-2h; In the described sequestrant preprocessing process, the sequestrant of selecting is one or more in edta edta, diethyl pentetic acid DTPA, the Sodium hexametaphosphate 99; In the step of described alkaline hydrogen peroxide bleaching, temperature 80-100 ℃, bleaching time 2-4h starches dense 5-10%; In the described acid-treated step, sour consumption 2-3, temperature 30-45 ℃, time 1.5-3h; The sour reagent that described acid treatment is adopted is one or more in sulfuric acid, hydrochloric acid or the nitric acid.
Preferably, also comprise formic acid and acetic acid steam condensation that evaporation is obtained in the described step (5), and be back in the reactor of step (1), be used for the step of the boiling of step (1).
Preferably, comprise also in the described step (3) that the liquid that solid-liquid separation is for the third time obtained carries out water acid rectifying, the formic acid that obtains and the mix acid liquor of acetic acid are back in the reactor of step (1), the step that is used for the boiling of step (1), and the water that obtains is back to step (3) as washing water.
Preferably, also comprise in the described step (6) liquid that the 4th time solid-liquid separation obtains is purified, the purification liquid that obtains concentration and be 5-10% is back to step (6) as organic solvent, and the liquid phase that the 5th time solid-liquid separation obtains in the impurity after the described purification and the described step (8) mixes.
Preferably, in the described step (1), the solid-liquid mass ratio is 1:8-1:12, temperature of reaction 120-145 ℃, and reaction times 20-40min; The total acid of described organic acid solution is dense to be 70-90%, and the mass ratio of acetic acid and formic acid is 1:1-1:8, and the quality that adds hydrogen peroxide accounts for the 1-6% of biomass material quality.
Preferably, in the described step (2), the solid-liquid mass ratio is 1:8-1:10.
Preferably, in the described step (3), starching dense is 4-6%; The water washing process of described step (3) is the adverse current water washing process.
Preferably, the adding quality of described organic solvent be described concentrated solution quality 2-5 doubly; Described organic solvent is ether, sherwood oil, methyl tertiary butyl ether, tetrabutyl urea or tri-tert amine.
Preferably, described Mierocrystalline cellulose is dissolving pulp and/or industrial fiber element.
Described biomass material is one or more in the wooden classes such as reed, beanstalk stalk, wheat stalk, straw, maize straw, melon seed cases, bamboo chip, melon seeds bar or the grass as raw material.
Technique scheme of the present invention has the following advantages compared to existing technology:
1, the first time that will collect of technique of the present invention and for the second time the liquid that obtains of solid-liquid separation directly evaporate and obtain formic acid, acetic acid vapor, and make and be used in the cooking reaction that directly is back to the first step after its condensation recycling, and since formic acid and acetic acid re-use as raw material, boiling efficiency to biomass is higher, for the technique of the circulation of the cooking liquor after utilizing boiling, although saved the step of this circulation, but realized within the identical process time, higher to the extraction efficiency of each component;
2, after the technique the first step of the present invention boiling and the pentose solution of collecting behind the acid elution directly evaporate, evaporate formic acid and acetic acid, can be used on the one hand the circulation of raw material, also reduce simultaneously the acid content in the pentose solution as far as possible, avoid occuring esterification, keep to greatest extent boiling and obtain pentose solution;
3, digestion process of the present invention carries out in airtight reaction vessel, because the evaporation of the part of formic acid, acetic acid and hydrogen peroxide, so that have certain pressure in the container, thus shortened the cooking time of raw material, reduced cellulosic destruction.
4, process selection formic acid of the present invention, the common boiling biomass material of acetic acid; formic acid is as a kind of strong organic acid; urge the xylogen of doing in the degraded raw material; because use formic acid can destroy the alpha-cellulose in the Mierocrystalline cellulose separately; not only protected alpha-cellulose not to be destroyed so add an amount of acetic acid; and the organic solvent dissolution lignin molecule that utilizes formic acid and acetic acid to form; also utilize its acid boiling hemicellulose wherein, and with this with Mierocrystalline cellulose, hemicellulose and lignin separation.
5, adding hydrogen peroxide in the cooking liquor of the present invention is catalyzer, so that the xylogen of biomass material middle-shallow layer and hemicellulose and HO
+Ionic reaction, constantly dissolved, and HO
+Little on cellulosic impact, after for some time, HO
+Ion consumption is complete, H
+The activity of ion increases greatly, so that hemicellulose removes rapidly with the xylogen that is soluble in acid.Thereby improved the extraction yield of xylogen.
5, after for the first time boiling obtained Mierocrystalline cellulose, the organic acid solution that continues to adopt formic acid, acetic acid and hydrogen peroxide to form carried out pickling to Mierocrystalline cellulose, on the one hand the inner remaining hemicellulose of Mierocrystalline cellulose and xylogen was decomposed and stripping, guaranteed simultaneously cellulosic purity;
6, before separating out xylogen, the adding auxiliary agent evaporates formic acid and acetic acid, the circulating reaction that the formic acid that steams on the one hand and acetic acid can be used for the boiling step is to economize in raw materials, simultaneously except behind the formic acid removal, acetic acid concentration, guarantee that auxiliary agent with minimum dose is so that xylogen is all separated out energy efficient;
7, this processing step liquid that solid-liquid separation is obtained evaporates and dissolving xylogen and the pentose solution wherein when having greatly reduced direct reuse of purifying, and has improved the purity of xylogen.
8, the auxiliary agent that adds in the concentrated solution, be a kind of dissolve each other with formic acid but with the immiscible low polarity auxiliary agent of water, add described auxiliary agent after, lignin and wood sugar in the concentrated solution are separated out together, recycling moisture obtains respectively highly purified lignin from the lignin with wood sugar.
9, the reaction times of described dehydration carburizing reagent longer, guarantee the transformation efficiency of furfural, the present invention produces in the process of furfural, the dehydration carburizing reagent is in the preparation furfural, also obtain the by product biological carbon, not only reduced environmental pollution, can also create more income for furfural enterprise.
10, furfural is heat-sensitive substance, polymerization easily occurs and being deposited on the equipment, not only affect in the course of time the efficient of equipment, also affects the productive rate of furfural, monocalcium phosphate, potassium primary phosphate can play the effect of inhibition in the acid catalyzer of the present invention, can effectively prevent the polymerization of furfural.
11, acid catalyzer of the present invention is little to the corrodibility of equipment, can come producing apparatus with common stainless steel, and the device fabrication cost is low, and plant investment is little.
Description of drawings
For content of the present invention is more likely to be clearly understood, the below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is the schema of technique of the present invention.
Embodiment
The below will the invention will be further described by specific embodiment.
In this application, except specified otherwise was arranged, used percentage composition all represented the quality percentage composition, i.e. " % " expression " wt% "; In described organic acid solution or the mix acid liquor except a certain amount of formic acid, acetic acid, surplus is water, the total mass of the dense nail acid of the total acid of organic acid solution and acetic acid accounts for the percentage ratio of described organic acid solution quality, the formic acid that adds in the dense finger acid pickling step of the total acid of mix acid liquor and the total mass of acetic acid account for the percentage ratio of described mix acid liquor quality
Slurry described in each step is dense=this step in the quality and * 100% of solid and liquid in the quality/this step of solid
Hydrogen peroxide H among each embodiment
2O
2Form take the aqueous hydrogen peroxide solution of mass concentration as 27% adds.For example need as calculated to add the 2.7g hydrogen peroxide, then corresponding should be to add 10g(2.7 ÷ 0.27=10) described aqueous hydrogen peroxide solution.
The measuring brightness method of cellulose/paper slurry is with reference to FZ/T500107-1998, the alpha-cellulose content measuring method is with reference to FZ/T500104-1998, polymerization degree measurement adopts the Fz/T500103-1998 method, the FZ/T500105-1998 method is adopted in determination of ash, inhale base number and measure employing FZ/T500109-1998 method, the measuring method GB/T3332-2004 of beating degree.
The assay of fixed carbon, ash content and moisture adopts coal industrial analysis method GB/T212-2008 to measure in the biological carbon, the mensuration of sulphur content adopts the measuring method GB/T214-2007 of full content of Sulphur in coal to measure, and the heat output determining method of biological carbon adopts the heat output determining method GB/T213-2008 of coal.Solids content adopts halogen fast tester for water content (plum Teller-Tuo benefit, model: HB43-S) measure under 115 ℃.The concentration of pentose or xylose solution adopts high-efficient liquid phase color instrument (model: U-3000, producer: measure ThermoFisher Dai An company).
Among each embodiment,
The quality of biological carbon yield=biological carbon/(the solids content) ╳ 100% of the amount of the liquid of participation reaction * this liquid
The Zhi Liang ╳ 100% of cellulosic productive rate=cellulosic quality/raw material.
Furfural content % in furfural yield=furfural stock solution quality * liquid/(liquid glucose quality * liquid glucose furfural content %) * 100%.
The extraction yield %=pentose solution quality of hemicellulose * pentose concentration/(hemicellulose level in raw materials quality * raw material) * 100%;
Lignin extraction rate=xylogen quality/(content of xylogen in raw materials quality * raw material) * 100%.
Embodiment 1
In the present embodiment, described biomass material is reed (mass component forms: Mierocrystalline cellulose 49.5%, hemicellulose level 22.7%, xylogen 18.9%), at first the reed raw material is smashed, and washing dedusting with water and being crushed to particle diameter is 0.5-20cm.
Present embodiment comprises the steps: from the comprehensive utilization process of described biomass material
(1) with behind the biomass material comminution pretreatment, using total acid concentration is that the organic acid solution of 60% formic acid and acetic acid carries out boiling to the biomass material after processing, the mass ratio of acetic acid and formic acid is 1:1 in the organic acid solution of present embodiment, and adds the hydrogen peroxide (H that accounts for biomass material 1% before adding biomass material
2O
2) as catalyzer, 80 ℃ of control temperature of reaction, reaction 10min, the solid-liquid mass ratio is 1:5, and the reaction solution that obtains is carried out the solid-liquid separation first time;
(2) for the first time the solid that obtains of solid-liquid separation to add total acid concentration be that 75% formic acid and the organic acid solution of acetic acid carry out acid elution, wherein above-mentioned total acid concentration is to have added the hydrogen peroxide (H that accounts for biomass material 1% in 75% the organic acid solution
2O
2) be 1:1 as the mass ratio of catalyzer and acetic acid and formic acid, the control temperature is 20 ℃, washing time 1h, solid-liquid mass ratio are 1:10, and reaction solution is carried out the solid-liquid separation second time;
(3) collect in step (1) and the step (2) liquid that twice solid-liquid separation obtains, in 110 ℃, carry out underpressure distillation under the 301kpa, the steam and the solids content that obtain formic acid and acetic acid are 60% concentrated solution, and with formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that the described second time, solid-liquid separation obtained, and wash, the control washing temperature is 60 ℃, and starching dense is 4%, and the washing slurry that obtains is carried out for the third time solid-liquid separation;
(5) collect the liquid that solid-liquid separation for the third time obtains, carry out water, sour rectifying, the mix acid liquor that obtains is back to the boiling that is used for step (1) in the reactor of step (1) as cooking liquor, and the water that obtains is back to step (4) and washes water with water;
(6) collect solid and the screening that solid-liquid separation for the third time obtains and obtain the screened stock Mierocrystalline cellulose, the screened stock Mierocrystalline cellulose that obtains is bleached obtained Mierocrystalline cellulose; Its whiteness of Mierocrystalline cellulose that adopts after measured the method for present embodiment to obtain is 93%ISO, alpha-cellulose content 93%, and ash content 0.02%, the polymerization degree 400 is inhaled base number 650, productive rate 40%.
(7) concentrated solution of gained in the step (3) is added the organic solvent ether that accounts for 2 times of concentrated solution quality and analyse xylogen, the organic solvent ether that the low polarity of adding and water dissolve each other can reduce the polarity of whole system, and xylogen is separated out, carry out solid-liquid separation the 4th time, the described liquid that the 4th time solid-liquid separation obtains is purified, and obtains concentration and is 5% purification liquid and be back to step (7) as organic solvent.
(8) the solid thin up (the mass ratio 1:1 of solid and water) that obtains of described the 4th solid-liquid separation, and carry out solid-liquid separation the 5th time, the solid that obtains is xylogen, the extraction yield of its xylogen is 90%.
The liquid that (9) the 5th times solid-liquid separation obtains is pentose solution, the extraction yield of its hemicellulose is 85%, the impurity phase that described pentose solution and step (7) obtain after purifying mixes, under the katalysis of sodium pyrosulfate, the carburizing reagent 90min that under 170 ℃, dewaters, the consumption of sodium pyrosulfate is 0.05% of pentose solution quality, react complete after, reaction solution carries out solid-liquid separation the 5th time, and the liquid that obtains is furfural stoste.If the purer furfural that need obtain only needs to adopt the ordinary method made from extra care furfural in the prior art, furfural stoste is got final product by distillation tower is refining.The yield of furfural was 65% after reaction finished.
The solid that obtains after described the 5th solid-liquid separation is biological carbon, and its yield is 50%, and the fixed carbon content of described biological carbon is 56% after measured, ash oontent 0.12%, sulphur content 0.1%, moisture 41%, thermal value 4126J/g.
Bleaching described in the present embodiment may further comprise the steps:
(1) will at first carry out alkaline purification with the sodium hydroxide that accounts for screened stock Mierocrystalline cellulose quality 1% through the screened stock Mierocrystalline cellulose of screening, the control temperature is 50 ℃, and extracting time 0.5h starches dense 5%;
(2) carry out the sequestrant pre-treatment after alkaline purification, to adopt EDTA, its consumption to account for screened stock cellulosic 0.1% for sequestrant in the present embodiment, and the pH value is controlled between the 2-4, temperature 50 C, and time 0.5h starches dense 4%;
(3) carry out alkaline hydrogen peroxide bleaching after the EDTA pre-treatment, the consumption of hydrogen peroxide is that screened stock is cellulosic 3% again, and regulates the pH value between 10-12 with sodium hydroxide, temperature 70 C, and bleaching time 1h starches dense 5%; With
(4) utilize hydrochloric acid to carry out acid treatment, the hydrochloric acid consumption is that screened stock is cellulosic 6%, and the pH value is controlled between the 2-4,20 ℃ of temperature, and time 0.5h starches dense 3%.
Embodiment 2
In the present embodiment, at first straw (mass component forms: mass component forms: Mierocrystalline cellulose 35.8%, hemicellulose 28.6%, xylogen 14.3%) is smashed,, being crushed to particle diameter is 2cm ~ 10cm.
Present embodiment comprises the steps: from the comprehensive utilization process of described straw
(1) with behind the straw comminution pretreatment, using total acid concentration is that the organic acid solution of 65% formic acid and acetic acid carries out boiling to the reed after processing, the mass ratio of acetic acid and formic acid is 1:6 in the organic acid solution of present embodiment, and adds the hydrogen peroxide (H that accounts for straw raw material 2% before adding straw raw material
2O
2) as catalyzer, 100 ℃ of control temperature of reaction, reaction 20min, the solid-liquid mass ratio is 1:8, and the reaction solution that obtains is carried out the solid-liquid separation first time;
(2) for the first time the solid that obtains of solid-liquid separation to add total acid concentration be that 78% formic acid and the organic acid solution of acetic acid carry out acid elution, wherein above-mentioned total acid concentration is to have added the hydrogen peroxide (H that accounts for straw raw material 2% in 78% the organic acid solution
2O
2) be 1:3 as the mass ratio of catalyzer and acetic acid and formic acid, the control temperature is 25 ℃, washing time 50min, solid-liquid mass ratio are 1:4, and reaction solution is carried out the solid-liquid separation second time;
(3) collect in step (1) and the step (2) liquid that twice solid-liquid separation obtains, at 130 ℃, carry out underpressure distillation under the 580kpa, the steam and the solids content that obtain formic acid and acetic acid are 70% concentrated solution, and with formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that the second time, solid-liquid separation obtained, and wash, the control washing temperature is 65 ℃, and starching dense is 5%, and the washing slurry that obtains is carried out for the third time solid-liquid separation;
(5) collect the liquid that solid-liquid separation for the third time obtains, carry out water, sour rectifying, the mix acid liquor that obtains is back to the boiling that is used for step (1) in the reactor of step (1) as cooking liquor, and the water that obtains is back to step (5) and washes water with water;
(6) collect solid and the screening that solid-liquid separation for the third time obtains and obtain the screened stock Mierocrystalline cellulose, the screened stock Mierocrystalline cellulose that obtains is bleached obtained Mierocrystalline cellulose; Its whiteness of Mierocrystalline cellulose that adopts after measured the method for present embodiment to obtain is 92%ISO, alpha-cellulose content 92.5%, and ash content 0.04%, the polymerization degree 450 is inhaled base number 660, productive rate 23%.
(7) concentrated solution with gained in the step (3) adds the organic solvent ether that accounts for 5 times of concentrated solution quality, and carry out solid-liquid separation the 4th time, the described liquid that the 4th time solid-liquid separation obtains is purified, and obtains concentration and is 6% purification liquid and be back to step (4) as organic solvent.
(8) the solid thin up (the mass ratio 1:2 of solid and water) that obtains of described the 4th solid-liquid separation, and carry out solid-liquid separation the 5th time, the solid that obtains is xylogen, the extraction yield of its xylogen is 91%.
The liquid that (9) the 5th times solid-liquid separation obtains is pentose solution, the extraction yield of its hemicellulose is 85%, the impurity phase that described pentose solution obtains after purifying with step (7) is middle mixes, under the katalysis of sodium pyrosulfate, the carburizing reagent 120min that under 180 ℃, dewaters, the consumption of sodium pyrosulfate is 0.45% of pentose solution quality, react complete after, reaction solution carries out solid-liquid separation the 6th time, and the liquid that obtains is furfural stoste.If the purer furfural that need obtain only needs to adopt the ordinary method made from extra care furfural in the prior art, furfural stoste is got final product by distillation tower is refining.The yield of furfural was 63% after reaction finished.
The solid that obtains after described the 6th solid-liquid separation is biological carbon, and its yield is 52%, and the fixed carbon content of described biological carbon is 57% after measured, ash oontent 0.13%, sulphur content 0.05%, moisture 42%, thermal value 4762J/g.
Bleaching described in the present embodiment may further comprise the steps:
(1) will at first utilize the potassium hydroxide that accounts for screened stock Mierocrystalline cellulose 2% to carry out alkaline purification through the screened stock Mierocrystalline cellulose of screening, the control temperature be 70 ℃, and extracting time 1h starches dense 6%;
(2) carry out the sequestrant pre-treatment after alkaline purification, sequestrant adopts the DTPA(diethyl pentetic acid in the present embodiment, and its consumption accounts for 0.5% of screened stock Mierocrystalline cellulose quality, and the pH value is controlled between the 2-4,65 ℃ of temperature, and time 1h starches dense 6%;
(3) carry out alkaline hydrogen peroxide bleaching after the DTPA pre-treatment, the consumption of hydrogen peroxide is 4% of screened stock Mierocrystalline cellulose quality again, and regulates the pH value between 10-12 with sodium hydroxide, 80 ℃ of temperature, and bleaching time 2h starches dense 10%; With
(4) utilize sulfuric acid to carry out acid treatment, the consumption of sulfuric acid is 2% sulfuric acid of screened stock Mierocrystalline cellulose quality in this step, and the pH value is controlled between the 2-4,30 ℃ of temperature, and time 1h starches dense 4%.
Embodiment 3
In the present embodiment, described biomass material is bamboo chip (mass component forms: Mierocrystalline cellulose 47.3%, hemicellulose 24.6%, xylogen 25.8%), at first will smash, and washing dedusting with water and being crushed to particle diameter is 0.5-20cm.
The comprehensive utilization process of the described bamboo chip of present embodiment comprises the steps:
(1) with behind the bamboo chip comminution pretreatment, using total acid concentration is that the organic acid solution of 70% formic acid and acetic acid carries out boiling to the bamboo chip after processing, the mass ratio of acetic acid and formic acid is 1:8 in the organic acid solution of present embodiment, and adds the hydrogen peroxide (H that accounts for straw raw material 4% before adding straw raw material
2O
2) as catalyzer, 120 ℃ of control temperature of reaction, reaction 30min, the solid-liquid mass ratio is 1:12, and the reaction solution that obtains is carried out the solid-liquid separation first time;
(2) for the first time the solid that obtains of solid-liquid separation to add total acid concentration be that 80% formic acid and the organic acid solution of acetic acid carry out acid elution, wherein above-mentioned total acid concentration is to have added the hydrogen peroxide (H that accounts for raw material 3% in 80% the organic acid solution
2O
2) be 1:6 as the mass ratio of catalyzer and acetic acid and formic acid, the control temperature is 40 ℃, washing time 80min, described 95% organic acid solution is 1:8 with the solid-liquid mass ratio of the solid that solid-liquid separation for the first time obtains, and reaction solution is carried out the solid-liquid separation second time;
(3) collect in step (1) and the step (2) liquid that twice solid-liquid separation obtains, at 150 ℃, carry out underpressure distillation under the 640kpa, the steam and the solids content that obtain formic acid and acetic acid are 80% concentrated solution, and with formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that solid-liquid separation for the second time obtains and washing, the control washing temperature is 75 ℃, and starching dense is 6%, and the washing slurry that obtains is carried out for the third time solid-liquid separation;
(5) collect the liquid that solid-liquid separation for the third time obtains, carry out water, sour rectifying, the mix acid liquor that obtains is back to the boiling that is used for step (1) in the reactor of step (1) as cooking liquor, and the water that obtains is back to step (4) and washes water with water;
(6) collect solid and the screening that solid-liquid separation for the third time obtains and obtain the screened stock Mierocrystalline cellulose, the screened stock Mierocrystalline cellulose that obtains is carried out bleaching process obtain Mierocrystalline cellulose; Its whiteness of Mierocrystalline cellulose that adopts after measured the method for present embodiment to obtain is 91.5%ISO, alpha-cellulose content 93.2%, and ash content 0.03%, the polymerization degree 550 is inhaled base number 720, productive rate 41%.
(7) concentrated solution with gained in the step (3) adds the organic solvent tri-tert amine that accounts for 3 times of concentrated solution quality, and carry out solid-liquid separation the 4th time, the described liquid that the 4th time solid-liquid separation obtains is purified, and obtains concentration and is 8% purification liquid and be back to step (7) as organic solvent.
(8) the solid thin up (the mass ratio 1:2 of solid and water) that obtains of described the 4th solid-liquid separation, and carry out solid-liquid separation the 5th time, the solid that obtains is xylogen, the extraction yield of its xylogen is 92%.。
The liquid that (9) the 5th times solid-liquid separation obtains is pentose solution, the extraction yield of its hemicellulose is 90%, the impurity phase that described pentose solution and described step (7) obtain after purifying mixes, under the katalysis of sodium pyrosulfate, the carburizing reagent 100min that under 190 ℃, dewaters, the consumption of sodium pyrosulfate is 0.5% of pentose solution, react complete after, reaction solution carries out solid-liquid separation the 6th time, and the liquid that obtains is furfural stoste.If the purer furfural that need obtain only needs to adopt the ordinary method made from extra care furfural in the prior art, furfural stoste is got final product by distillation tower is refining.The yield of furfural was 65% after reaction finished.
The solid that obtains after described the 6th solid-liquid separation is biological carbon, and its yield is 55%, and the fixed carbon content of described biological carbon is 59.2% after measured, ash oontent 0.14%, and sulphur content 0.06%, moisture 40.5%, thermal value is 5230J/g.
Bleaching described in the present embodiment may further comprise the steps:
(1) will at first utilize 3% the potassium hydroxide that accounts for screened stock Mierocrystalline cellulose quality to carry out alkaline purification through the screened stock Mierocrystalline cellulose of screening, the control temperature be 85 ℃, and extracting time 2h starches dense 8%;
(2) after alkaline purification, carry out the sequestrant pre-treatment, in the present embodiment sequestrant adopt Sodium hexametaphosphate 99, its consumption account for screened stock Mierocrystalline cellulose quality 0.3%, the pH value is controlled between the 2-4,85 ℃ of temperature, time 1.5h starches dense 7%;
(3) after the Sodium hexametaphosphate 99 pre-treatment, carry out again alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is 5% of screened stock Mierocrystalline cellulose quality, and adopts sodium hydroxide to regulate the pH value between 10-12,85 ℃ of temperature, bleaching time 3h starches dense 8%; With
(4) acid treatment, the acid of adopting in this step is hydrochloric acid, and its consumption is 4% of screened stock Mierocrystalline cellulose quality, and the pH value is controlled between the 2-4,35 ℃ of temperature, time 1.5h starches dense 5%.
Embodiment 4
In the present embodiment, described biomass material is wheat straw (mass component forms: Mierocrystalline cellulose 40.5, hemicellulose 31.9%, xylogen 15.4%), at first will smash, and washing dedusting with water and being crushed to particle diameter is 0.5-20cm.
Present embodiment comprises the steps: from the comprehensive utilization process of described wheat straw
(1) with behind the wheat straw comminution pretreatment, using total acid concentration is that the organic acid solution of 80% formic acid and acetic acid carries out boiling to the bamboo chip after processing, the mass ratio of acetic acid and formic acid is 1:10 in the organic acid solution of present embodiment, and adds the hydrogen peroxide (H that accounts for wheat straw raw material 6% before adding raw material
2O
2) as catalyzer, 135 ℃ of control temperature of reaction, reaction 40min, the solid-liquid mass ratio is 1:10, and the reaction solution that obtains is carried out the solid-liquid separation first time;
(2) for the first time the solid that obtains of solid-liquid separation to add total acid concentration be that 84% formic acid and the organic acid solution of acetic acid carry out acid elution, wherein above-mentioned total acid concentration is to have added the hydrogen peroxide (H that accounts for wheat straw raw material 1.5% in 84% the organic acid solution
2O
2) be 1:9 as the mass ratio of catalyzer and acetic acid and formic acid, the control temperature is 45 ℃, washing time 1h, solid-liquid mass ratio are 1:16, and reaction solution is carried out the solid-liquid separation second time;
(3) collect in step (1) and the step (2) liquid that twice solid-liquid separation obtains, at 120 ℃, carry out underpressure distillation under the 390kpa, the steam and the solids content that obtain formic acid and acetic acid are 65% concentrated solution, and with formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that the second time, solid-liquid separation obtained, and wash, the control washing temperature is 85 ℃, and starching dense is 9%, and the washing slurry that obtains is carried out for the third time solid-liquid separation;
(5) collect the liquid that solid-liquid separation for the third time obtains, carry out water, sour rectifying, the mix acid liquor that obtains is back to the boiling that is used for step (1) in the reactor of step (1) as cooking liquor, and the water that obtains is back to step (4) and washes water with water;
(6) collect solid and the screening that solid-liquid separation for the third time obtains and obtain the screened stock Mierocrystalline cellulose, the screened stock Mierocrystalline cellulose that obtains is bleached obtained Mierocrystalline cellulose; Its whiteness of Mierocrystalline cellulose that adopts after measured the method for present embodiment to obtain is 92.5%ISO, alpha-cellulose content 92.6%, and ash content 0.16%, the polymerization degree 620 is inhaled base number 780, productive rate 32%.
(7) concentrated solution with gained in the step (3) adds the organic solvent tetrabutyl urea that accounts for 6 times of concentrated solution quality, and carry out solid-liquid separation the 4th time, the described liquid that the 4th time solid-liquid separation obtains is purified, and obtains concentration and is 7% purification liquid and be back to step (7) as organic solvent.
(8) the solid thin up (the mass ratio 1:3 of solid and water) that obtains of described the 4th solid-liquid separation, and carry out solid-liquid separation the 5th time, the solid that obtains is xylogen, the extraction yield of its xylogen is 88%.
The liquid that (9) the 5th times solid-liquid separation obtains is pentose solution, the extraction yield of its hemicellulose is 95%, the impurity phase that described pentose solution and described step (7) obtain after purifying mixes, under the katalysis of sodium pyrosulfate, the carburizing reagent 140min that under 210 ℃, dewaters, the consumption of sodium pyrosulfate is 0.3% of pentose solution, react complete after, reaction solution carries out solid-liquid separation the 6th time, and the liquid that obtains is furfural stoste.If the purer furfural that need obtain only needs to adopt the ordinary method made from extra care furfural in the prior art, furfural stoste is got final product by distillation tower is refining.The yield of furfural was 64% after reaction finished.
The solid that obtains after described the 6th solid-liquid separation is biological carbon, and its yield is 54%, and the fixed carbon content of described biological carbon is 55.8% after measured, ash oontent 0.08%, sulphur content 0.08%, moisture 44%, thermal value 5012J/g.
Bleaching described in the present embodiment may further comprise the steps:
(1) will at first utilize 5% the sodium hydroxide that accounts for screened stock Mierocrystalline cellulose quality to carry out alkaline purification through the screened stock Mierocrystalline cellulose of screening, the control temperature be 90 ℃, and extracting time 3h starches dense 10%;
(2) carry out the sequestrant pre-treatment after alkaline purification, sequestrant adopts Sodium hexametaphosphate 99 in the present embodiment, and its consumption accounts for 1% of screened stock Mierocrystalline cellulose quality, and the pH value is controlled between the 2-4, temperature 70 C, and time 130min starches dense 5%;
(3) after the Sodium hexametaphosphate 99 pre-treatment, carry out again alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is 6% of screened stock Mierocrystalline cellulose quality, and utilizes sodium hydroxide control pH value between 10-12,95 ℃ of temperature, bleaching time 4h starches dense 12%;
(4) utilize nitric acid to carry out acid treatment, nitric acid dosage is 1% of screened stock Mierocrystalline cellulose quality in this step, and the pH value is controlled between the 2-4,40 ℃ of temperature, and time 2h starches dense 6%.
Embodiment 5
In the present embodiment, described biomass material is melon seeds bar (mass component forms: hemicellulose 31.91%, xylogen 23.94%, Mierocrystalline cellulose 44.15%), at first the melon seeds bar is smashed, and washing dedusting with water and being crushed to particle diameter is 0.5-20cm.
Present embodiment comprises the steps: from the comprehensive utilization process of described melon seeds bar
(1) with behind the melon seeds bar comminution pretreatment, using total acid concentration is that the organic acid solution of 90% formic acid and acetic acid carries out boiling to the melon seeds bar after processing, the mass ratio of acetic acid and formic acid is 1:13 in the organic acid solution of present embodiment, and adds the hydrogen peroxide (H that accounts for melon seeds bar raw material 7% before adding melon seeds bar raw material
2O
2) as catalyzer, 140 ℃ of control temperature of reaction, reaction 50min, the solid-liquid mass ratio of described organic acid solution and melon seeds bar raw material is 1:20, and the reaction solution that obtains is carried out the solid-liquid separation first time;
(2) for the first time the solid that obtains of solid-liquid separation to add total acid concentration be that 90% formic acid and the organic acid solution of acetic acid carry out acid elution, wherein above-mentioned total acid concentration is to have added the hydrogen peroxide (H that accounts for melon seeds bar raw material 2.5% in 90% the organic acid solution
2O
2) be 1:10 as the mass ratio of catalyzer and acetic acid and formic acid, the control temperature is 50 ℃, washing time 40min, solid-liquid mass ratio are 1:12, and reaction solution is carried out the solid-liquid separation second time;
(3) collect in step (1) and the step (2) liquid that twice solid-liquid separation obtains, at 160 ℃, carry out underpressure distillation under the 510kpa, the steam and the solids content that obtain formic acid and acetic acid are 75% concentrated solution, and with formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that the second time, solid-liquid separation obtained, and wash, the control washing temperature is 90 ℃, and starching dense is 10%, and the washing slurry that obtains is carried out for the third time solid-liquid separation;
(5) collect the liquid that solid-liquid separation for the third time obtains, carry out water, sour rectifying, the mix acid liquor that obtains is back to the boiling that is used for step (1) in the reactor of step (1) as cooking liquor, and the water that obtains is back to step (4) and washes water with water;
(6) collect solid and the screening that solid-liquid separation for the third time obtains and obtain the screened stock Mierocrystalline cellulose, the screened stock Mierocrystalline cellulose that obtains is bleached obtained Mierocrystalline cellulose; Its whiteness of Mierocrystalline cellulose that adopts after measured the method for present embodiment to obtain is 91%ISO, alpha-cellulose content 94%, and ash content 0.08%, the polymerization degree 660 is inhaled base number 620, productive rate 33%.
(7) concentrated solution with gained in the step (3) adds the organic solvent methyl tertiary butyl ether that accounts for 8 times of concentrated solution quality, and carry out solid-liquid separation the 4th time, the described liquid that the 4th time solid-liquid separation obtains is purified, and obtains concentration and is 9% purification liquid and be back to step (7) as organic solvent.
(8) the solid thin up (the mass ratio 1:7 of solid and water) that obtains of described the 4th solid-liquid separation, and carry out solid-liquid separation the 5th time, the solid that obtains is xylogen, the extraction yield of its xylogen is 86.7%.
The liquid that (9) the 5th times solid-liquid separation obtains is pentose solution, the extraction yield of its hemicellulose is 92%, the impurity phase that described pentose solution and described step (7) obtain after purifying mixes, under the katalysis of sodium pyrosulfate, the carburizing reagent 180min that under 220 ℃, dewaters, wherein the sodium pyrosulfate consumption is 0.4% of pentose solution quality, react complete after, reaction solution carries out solid-liquid separation the 6th time, and the liquid that obtains is furfural stoste.If the purer furfural that need obtain only needs to adopt the ordinary method made from extra care furfural in the prior art, furfural stoste is got final product by distillation tower is refining.The yield of furfural was 60% after reaction finished.
The solid that obtains after described the 6th solid-liquid separation is biological carbon, and its yield is 56%, and the fixed carbon content of described biological carbon is 49.5% after measured, ash oontent 0.06%, sulphur content 0.05%, moisture 50%, thermal value 3900J/g.
Bleaching described in the present embodiment may further comprise the steps:
(1) will at first utilize the sodium hydroxide that accounts for screened stock Mierocrystalline cellulose 6% to carry out alkaline purification through the screened stock Mierocrystalline cellulose of screening, the control temperature be 95 ℃, and extracting time 4h starches dense 13%;
(2) carry out the sequestrant pre-treatment after alkaline purification, sequestrant adopts the EDTA ethylenediamine tetraacetic acid (EDTA) in the present embodiment, and its consumption accounts for that screened stock is cellulosic 2.5%, and the pH value is controlled between the 2-4,55 ℃ of temperature, and time 100min starches dense 6.4%;
(3) after the Sodium hexametaphosphate 99 pre-treatment, carry out again alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is 3.5%, and controls the pH value between 10-12 with sodium hydroxide, 100 ℃ of temperature, bleaching time 6h starches dense 15%; With
(4) utilize sulfuric acid to carry out acid treatment, the sulfuric acid consumption is that screened stock is cellulosic 3% in this step,
Control the pH value between 2-4, temperature 45 C, time 3h starches dense 5.5%.
Embodiment 6
In the present embodiment, described biomass material is cotton stem (mass component forms: hemicellulose 22.1%, xylogen 23.3%, Mierocrystalline cellulose 54.5%), at first cotton stem is smashed, and washing dedusting with water and being crushed to particle diameter is 0.5-20cm.
The comprehensive utilization process of the described cotton stem of present embodiment comprises the steps:
(1) with behind the cotton stem comminution pretreatment, using total acid concentration is that the organic acid solution of 95% formic acid and acetic acid carries out boiling to the cotton stem after processing, the mass ratio of acetic acid and formic acid is 1:15 in the organic acid solution of present embodiment, and adds the hydrogen peroxide (H that accounts for cotton stem raw material 8% before adding raw material
2O
2) as catalyzer, 130 ℃ of control temperature of reaction, reaction 60min, the solid-liquid mass ratio is 1:25, and the reaction solution that obtains is carried out the solid-liquid separation first time;
(2) for the first time the solid that obtains of solid-liquid separation to add total acid concentration be that 95% formic acid and the organic acid solution of acetic acid carry out acid elution, wherein above-mentioned total acid concentration is to have added the hydrogen peroxide (H that accounts for raw material 3% in 95% the organic acid solution
2O
2) be 1:15 as the mass ratio of catalyzer and acetic acid and formic acid, the control temperature is 60 ℃, washing time 20min, solid-liquid mass ratio are 1:20, and reaction solution is carried out the solid-liquid separation second time;
(3) collect in step (1) and the step (2) liquid that twice solid-liquid separation obtains, at 140 ℃, carry out underpressure distillation under the 701kpa, the steam and the solids content that obtain formic acid and acetic acid are 90% concentrated solution, and with formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that the second time, solid-liquid separation obtained, and wash, the control washing temperature is 88 ℃, and washing slurry is dense to be 1%, and the washing slurry that obtains is carried out for the third time solid-liquid separation;
(5) collect the liquid that solid-liquid separation for the third time obtains, carry out water, sour rectifying, the mix acid liquor that obtains is back to the boiling that is used for step (1) in the reactor of step (1) as cooking liquor, and the water that obtains is back to step (4) and washes water with water;
(6) collect solid and the screening that solid-liquid separation for the third time obtains and obtain the screened stock Mierocrystalline cellulose, the screened stock Mierocrystalline cellulose that obtains is bleached obtained Mierocrystalline cellulose; Its whiteness of Mierocrystalline cellulose that adopts after measured the method for present embodiment to obtain is 90%ISO, alpha-cellulose content 94.5%, and ash content 0.1%, the polymerization degree 700 is inhaled base number 780, productive rate 40%.
(7) concentrated solution of gained in the step (3) is added the organic solvent sherwood oil of 9 times of concentrated solution quality, and carry out solid-liquid separation the 4th time, the described liquid that the 4th time solid-liquid separation obtains is purified, and obtains 10% purification liquid and is back to step (4) as organic solvent.
(8) the solid thin up (the mass ratio 1:5 of solid and water) that obtains of described the 4th solid-liquid separation, and carry out solid-liquid separation the 5th time, the solid that obtains is xylogen, the extraction yield of its xylogen is 85%.
The liquid that (9) the 5th times solid-liquid separation obtains is pentose solution, the extraction yield of its hemicellulose is 94%, residual impurity mixed mutually after described pentose solution was purified with described step (7) is middle, under the katalysis of sodium pyrosulfate, the carburizing reagent 300min that under 200 ℃, dewaters, the sodium pyrosulfate consumption is 0.35% of pentose solution, react complete after, reaction solution carries out solid-liquid separation the 6th time, and the liquid that obtains is furfural stoste.If the purer furfural that need obtain only needs to adopt the ordinary method made from extra care furfural in the prior art, furfural stoste is got final product by distillation tower is refining.The yield of furfural was 62% after reaction finished.
The solid that obtains after described the 6th solid-liquid separation is biological carbon, and its yield is 60%, and the fixed carbon content of described biological carbon is 57.2% after measured, ash oontent 0.09%, sulphur content 0.05%, moisture 42%, 4923J/g.
Bleaching described in the present embodiment may further comprise the steps:
(1) will at first utilize the sodium hydroxide that accounts for screened stock Mierocrystalline cellulose 4% to carry out alkaline purification through the screened stock Mierocrystalline cellulose of screening, the control temperature be 100 ℃, and extracting time 3.5h starches dense 15%;
(2) carry out the sequestrant pre-treatment after alkaline purification, to adopt Sodium hexametaphosphate 99, its consumption to account for screened stock cellulosic 3% for sequestrant in the present embodiment, and the pH value is controlled between the 2-4, temperature 60 C, and time 2h starches dense 5.5%;
(3) after the Sodium hexametaphosphate 99 pre-treatment, carry out again alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is 4.5%, and is controlled between the 10-12 with sodium hydroxide adjusting pH value, 120 ℃ of temperature, bleaching time 2.5h starches dense 20%; With
(4) utilize sulfuric acid to carry out acid treatment, the sulfuric acid consumption is that screened stock is cellulosic 5% in this step, and the pH value is controlled between the 2-4,25 ℃ of temperature, and time 2.5h starches dense 4.5%.
Obviously, above-described embodiment only is for example clearly is described, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give all embodiments exhaustive.And the apparent variation of being extended out thus or change still are among the protection domain of the invention.
Claims (14)
1. the comprehensive utilization process of a biomass material is characterized in that, comprises the steps:
(1) with after the biomass material pulverizing, under the katalysis of hydrogen peroxide, use is carried out boiling by the organic acid solution that formic acid, acetic acid form to described raw material, 80-145 ℃ of control boiling temperature, the solid-liquid mass ratio is 1:5-1:25, reaction times 10-60min, and the reaction solution that obtains carried out the solid-liquid separation first time;
In the described organic acid solution, total acid is dense to be 60-95%, and the mass ratio of described acetic acid and formic acid is 1:1-1:15, and surplus is water;
Hydrogen peroxide accounts for the 1-8% of biomass material;
(2) collect the solid that the described first time, solid-liquid separation obtained, under the katalysis of hydrogen peroxide, the mix acid liquor that adopts formic acid, acetic acid to form carries out pickling to described solid, 20-60 ℃ of control pickling temperature, the solid-liquid mass ratio is 1:4-1:20, and the reaction solution that obtains is carried out the solid-liquid separation second time; Hydrogen peroxide accounts for the 1-3% of biomass material, and the total acid of described mix acid liquor is dense to be 75-95%, and the mass ratio of acetic acid and formic acid is 1:1-1:15;
(3) collect the solid that the described second time, solid-liquid separation obtained, and wash, the control washing temperature is 60-90 ℃, and starching dense is 1-10%, and the washing slurry that obtains is carried out for the third time solid-liquid separation;
(4) collect solid and the screening that described for the third time solid-liquid separation obtains and obtain the screened stock Mierocrystalline cellulose, described screened stock Mierocrystalline cellulose obtains required Mierocrystalline cellulose after bleaching.
(5) collect step for the first time and the liquid that obtains of solid-liquid separation for the second time, at 110-160 ℃, evaporate under the 301-701kpa and obtain formic acid and acetic acid steam and concentrated solution, the solids content of described concentrated solution is 60wt%-90wt%;
(6) concentrated solution with gained in the step (5) adds organic solvent, stirs, and carries out solid-liquid separation the 4th time, and wherein, the adding quality of described organic solvent is 1-10 times of described concentrated solution quality;
(7) collect the solid thin up that obtains after the 4th solid-liquid separation and stir, and the solid that carries out obtaining after the 5th solid-liquid separation is required xylogen through washing;
(8) after described the 5th solid-liquid separation, after the liquid process dehydration carburizing reagent that obtains, carry out solid-liquid separation the 6th time, the solid that obtains is biological carbon, and the further rectifying of the liquid that obtains obtains the finished product furfural.
2. the comprehensive utilization process of biomass material according to claim 1 is characterized in that:
Described dehydration carburizing reagent, the control temperature of reaction is 170-220 ° of C, reaction times 90-300min, and add the acid saline catalyst, the consumption of described acid saline catalyst is the 0.05wt%-0.5wt% of the 5th liquid mass that solid-liquid separation obtains.
3. technique of producing furfural by biomass material according to claim 2 is characterized in that:
Described dehydration carburizing reagent, the control temperature of reaction is 170-190 ° of C, reaction times 90-180min.
4. technique of producing furfural by biomass material according to claim 3 is characterized in that:
Described acid saline catalyst is hydrosulfate, supercarbonate, hydrophosphate and dihydrogen phosphate.
5. the comprehensive utilization process of arbitrary described biomass material according to claim 1-4 is characterized in that:
Described bleaching comprises:
Alkaline purification, described alkali consumption accounts for the 1-6% of described screened stock Mierocrystalline cellulose quality, and temperature is 50-100 ℃, and extracting time 0.5-4h starches dense 5-15%;
Sequestrant pre-treatment, the quality of described sequestrant account for the 0.1-3% of described screened stock Mierocrystalline cellulose quality, and the pH value is controlled between the 2-4, and temperature 50-80 ℃, time 0.5-2h starches dense 4-7%;
Alkaline hydrogen peroxide bleaching, the quality of alkaline hydrogen peroxide account for the 3-6% of described screened stock Mierocrystalline cellulose quality, and the pH value is controlled between the 10-12, and temperature 70-120 ℃, bleaching time 1-6h starches dense 5-20%; With
Acid treatment, the quality of described acid account for the 1%-6% of described screened stock Mierocrystalline cellulose quality, and the pH value is controlled between the 2-4, and temperature 20-45 ℃, time 0.5-3h starches dense 3-6%.
6. the comprehensive utilization process of biomass material according to claim 5 is characterized in that:
In the step of described alkaline purification, described alkali consumption accounts for the 2-5% of described screened stock Mierocrystalline cellulose quality, and temperature is 85-95 ℃, and extracting time 1-3h starches dense 6-12%;
The alkali reagent that described alkaline purification process is selected is sodium hydroxide and/or potassium hydroxide;
State in the pretreated step of sequestrant, the quality of described sequestrant accounts for the 0.1-0.5% of described screened stock Mierocrystalline cellulose quality, temperature 50-65 ℃, time 1.5-2h;
In the described sequestrant preprocessing process, the sequestrant of selecting is one or more in edta edta, diethyl pentetic acid DTPA, the Sodium hexametaphosphate 99;
In the step of described alkaline hydrogen peroxide bleaching, temperature 80-100 ℃, bleaching time 2-4h starches dense 5-10%;
In the described acid-treated step, sour consumption 2-3, temperature 30-45 ℃, time 1.5-3h;
The sour reagent that described acid treatment is adopted is one or more in sulfuric acid, hydrochloric acid or the nitric acid.
7. the comprehensive utilization process of arbitrary described biomass material according to claim 1-6 is characterized in that:
Also comprise formic acid and acetic acid steam condensation that evaporation is obtained in the described step (5), and be back in the reactor of step (1), be used for the step of the boiling of step (1).
8. the comprehensive utilization process of arbitrary described biomass material according to claim 1-7 is characterized in that:
Comprise also in the described step (3) that the liquid that solid-liquid separation is for the third time obtained carries out water acid rectifying, the formic acid that obtains and the mix acid liquor of acetic acid are back in the reactor of step (1), the step that is used for the boiling of step (1), and the water that obtains is back to step (3) as washing water.
9. the comprehensive utilization process of arbitrary described biomass material according to claim 1-8 is characterized in that:
Also comprise in the described step (6) liquid that the 4th time solid-liquid separation obtains is purified, the purification liquid that obtains concentration and be 5-10% is back to step (6) as organic solvent, and the liquid phase that the 5th time solid-liquid separation obtains in the impurity after the described purification and the described step (8) mixes.
10. the comprehensive utilization process of biomass material according to claim 9 is characterized in that:
In the described step (1), the solid-liquid mass ratio is 1:8-1:12, temperature of reaction 120-145 ℃, and reaction times 20-40min;
The total acid of described organic acid solution is dense to be 70-90%, and the mass ratio of acetic acid and formic acid is 1:1-1:8, and the quality that adds hydrogen peroxide accounts for the 1-6% of biomass material quality.
11. the comprehensive utilization process of arbitrary described biomass material according to claim 1-12 is characterized in that:
In the described step (2), the solid-liquid mass ratio is 1:8-1:10.
12. the comprehensive utilization process of arbitrary described biomass material according to claim 1-11 is characterized in that:
In the described step (3), starching dense is 4-6%; The water washing process of described step (3) is the adverse current water washing process.
13. arbitrary described technique of extracting xylogen from biomass material according to claim 1-12 is characterized in that:
The adding quality of described organic solvent is 2-5 times of described concentrated solution quality;
Described organic solvent is ether, sherwood oil, methyl tertiary butyl ether, tetrabutyl urea or tri-tert amine.
14. the comprehensive utilization process of arbitrary described biomass material is characterized in that according to claim 1-13:
Described Mierocrystalline cellulose is dissolving pulp and/or industrial fiber element.
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| CN107345372A (en) * | 2016-05-05 | 2017-11-14 | 中国农业科学院农业环境与可持续发展研究所 | It is a kind of that cellulose nano-fibrous method is prepared based on biomass material |
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| CN103806318A (en) * | 2014-01-16 | 2014-05-21 | 北京林业大学 | Method for extracting cellulose from furfural residues |
| CN104894906A (en) * | 2015-05-29 | 2015-09-09 | 华南理工大学 | High-efficiency clean bleaching method of wheat straw pulp |
| CN107345372B (en) * | 2016-05-05 | 2019-05-28 | 中国农业科学院农业环境与可持续发展研究所 | A method of it is prepared based on biomass material cellulose nano-fibrous |
| CN107345372A (en) * | 2016-05-05 | 2017-11-14 | 中国农业科学院农业环境与可持续发展研究所 | It is a kind of that cellulose nano-fibrous method is prepared based on biomass material |
| CN105879849A (en) * | 2016-06-08 | 2016-08-24 | 四川大学 | Straw-based solid amine sulfur dioxide adsorbent and preparing and using methods thereof |
| CN105879849B (en) * | 2016-06-08 | 2018-02-16 | 四川大学 | Straw base solid amine sulfur dioxide adsorbent and its preparation and application |
| CN108166293A (en) * | 2017-12-04 | 2018-06-15 | 湖南省农业科学院 | The method and its system of a kind of irradiation-plant fibrous agricultural wastes of chemical method Combined Treatment |
| CN109322199A (en) * | 2018-09-28 | 2019-02-12 | 中国林业科学研究院林产化学工业研究所 | A kind of method of wood fibre full constituent comprehensive utilization |
| CN110684204A (en) * | 2019-09-23 | 2020-01-14 | 广东工业大学 | Method for separating wood fiber by organic acid and homologously preparing furfural |
| CN110983844A (en) * | 2019-12-31 | 2020-04-10 | 宏业生物科技股份有限公司 | Method for extracting cellulose and lignin by using biomass material and method for recovering formic acid and furfural by using residual liquid after extraction |
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| CN111871457B (en) * | 2020-06-29 | 2021-03-30 | 南京工业大学 | Catalytic liquid for straw biomass and continuous treatment process |
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