CN101696428A - Method for co-producing ethanol, cellulose and compound fertilizer by using crop straw as raw material - Google Patents
Method for co-producing ethanol, cellulose and compound fertilizer by using crop straw as raw material Download PDFInfo
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- CN101696428A CN101696428A CN200910229716A CN200910229716A CN101696428A CN 101696428 A CN101696428 A CN 101696428A CN 200910229716 A CN200910229716 A CN 200910229716A CN 200910229716 A CN200910229716 A CN 200910229716A CN 101696428 A CN101696428 A CN 101696428A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The invention discloses a method for co-producing ethanol, cellulose and compound fertilizer by using crop straws as a raw material, which comprises: adding coarsely ground crop straws and acidic aqueous solution of which the pH value is 2 to 4 in mass part ratio of 1:2-3 into a cooking kettle and heating the mixture to 60 to 90 DEG C to cook the mixture for 4 to 8 hours; squeezing reactants to obtain solution, neutralizing the solution, regulating the concentration of the solution to 15 to 25 percent, producing ethanol by the conventional fermentation process, washing the straw residues obtained after squeezing by clean water, using the liquid obtained after the washing in the feeding of next batch of raw material, washing and squeezing the resulting material again, and mixing the obtained straw residue with aqueous solution containing a lignin leaching agent in a mass part ratio of 1:6-8, heating the mixture to 60 to 90 DEG C for cooking the mixture for 4 to 8 hours, filtering the mixture to obtain a coarse product of cellulose, washing and bleaching the coarse product of cellulose, filtering the coarse product of cellulose under compression for dewatering and drying the coarse product of cellulose to obtain a finished product of cellulose, wherein the bleaching liquid is used in the reaction of the next batch of raw material; and concentrating residual liquid obtained after the extraction of ethanol and the filtration of the coarse product of cellulose, drying the concentrate by spray for granulation, and making the compound fertilizer. As the method can extract ethanol and coproduce the cellulose and the compound fertilizer, so the drawbacks of single product production, waster source waste and heavy environmental pollution in the prior art are avoided.
Description
Technical field:
The present invention relates to a kind of is the method for raw material co-producing ethanol, Mierocrystalline cellulose, composite fertilizer with the agricultural crop straw, and agricultural crop straw is meant this class of standing grain straws such as corn, Chinese sorghum, wheat straw.
Background technology:
Stalk process and utilization technologies such as existing corn, Chinese sorghum are varied: straw chopping and returning; Stalk is made Mierocrystalline cellulose (paper pulp); Stalk is made fertilizer, gac or feed; Straw power generation; Gasifying stalk; Bioenergy etc.These technology all are to extract, utilize the part material composition, do not embody the maximum value of raw material, the ubiquity raw material availability is low, product is single, value added by manufacture is few, the course of processing " three wastes " is serious, enterprise's direct benefit and problem such as social benefit is relatively poor, peasant's direct yield is little.Therefore, fail to solve on the whole the still major part problem that goes out of use, burn of agricultural crop straw.
Extract alcoholic acid technology as stalk fermentation, the difficult problem that the stalk remaining component can not be fully utilized fails to solve.Though can use the enzyme decomposition of cellulose, isolate the compositions that can be used for fermented extracted alcohol more, its cost is very high, and the alcohol of production also is unable to catch up with cellulosic marketable value, does not possess feasibility economically.
The pulping process of paper-making industry and for example.The plant that is generally used for pulping raw material can be divided into 4 big classes: stem fiber-like, phloem fiber class, seed hair fiber class and lumber fibre class.Wherein the lumber fibre class is most important, and present China timber resources far can not satisfy the needs of growing pulp and paper industry.In order to remedy the deficiency of raw material, every year will be from a considerable amount of paper pulp of external import.Traditional technology often adopts chemical method, is steaming-boiling agent with sodium hydroxide and sodium sulphite mixed solution etc., and the waste liquid after the boiling directly effluxes without utilization rationally, contains a large amount of chlorine, sulphur, sodium etc., causes serious environmental to pollute, and it is very high to administer pollution cost.
Therefore, study a kind of both big as far as possible alcohol that extracts, it is essential that reasonable again, the high-quality technical matters of isolating other compositions such as stalk institute cellulose becomes.
Summary of the invention:
The purpose of this invention is to provide a kind of is the method for raw material co-producing ethanol, Mierocrystalline cellulose, composite fertilizer with the agricultural crop straw, except that extracting the ethanol, but also coproduction Mierocrystalline cellulose, composite fertilizer, having changed domestic existing ethanol fermentation extractive technique can only a kind of product of single production, the drawback of water resource waste and serious environment pollution.
The objective of the invention is to realize with following steps:
A, will be the agricultural crop straw raw material of coarse crushing and the acidic aqueous solution that the pH value transfers to 2-4 put in the digester by 1 part of mass ratio 2-3 part, being heated to 60-90 ℃ under the normal pressure carried out boiling 4-8 hour;
B, with reactant squeezing, the solution that obtains after the squeezing, is adjusted concentration 15-25% at neutralization, zymotechnique is produced ethanol routinely;
The stalk residue that obtains after c, the squeezing washes with the clear water of stalk 2-3 times quality in the relative a step, squeezing the stalk residue that obtains after the flushing again mixes by 1 part of mass ratio to 6-8 part with the aqueous solution that contains the agent of xylogen solution-off, be heated to 60-90 ℃ under the normal pressure and carried out boiling 4-8 hour, filter coarse product of cellulose;
Wherein: the agent of used xylogen solution-off is made of potassiumphosphate 7-8 mass parts, potassium permanganate 1.9-2.9 mass parts, timber permeate agent 0.1 mass parts, and the agent of xylogen solution-off accounts for 0.1-0.5% by quality in the aqueous solution of xylogen solution-off agent;
D, the b step has been extracted the surplus liquid of alcoholic acid and c step filtered to such an extent that the surplus liquid after the coarse product of cellulose concentrates, sprays dried granulation, made composite fertilizer.
Acidic aqueous solution in the above a step is aqueous sulfuric acid or aqueous hydrochloric acid.
Coarse product of cellulose in the above c step promptly gets cellulose finished product through cleaning bleaching, filter-press dehydration, oven dry.
Rinsing liquid is as carrying out needed acidic aqueous solution preparation composition in a step in later batch rinsing liquid or the production process.
In the above c step, the stalk residue is washed with clear water, the liquid that the squeezing back extrudes is as carrying out needed acidic aqueous solution preparation composition in a step in the batch production process later on.
In a step, being used for the acidic aqueous solution of boiling agricultural crop straw raw material, is the solution that forms behind clear water, last time or cooking liquor several times or the flushing squeezing stalk, one or both in them, three kinds mixed solution, the solution that is deployed into acid.
Wash-down water is used for the reaction to the following batch raw material of stalk, and rinse water are used for the reaction to the following batch raw material of stalk when being used for the rinsing of coarse product of cellulose or reaching finite concentration, and wash-down water and rinse water are reused.This process characteristic is water saving, and total fluid volume reduces significantly, and the ethanol in the solution, inorganic salt (being composite fertilizer's composition) concentration extraction more economically come out.
The present invention has compared following characteristics and progress with traditional technology: (1) primary first-order equation separation and Extraction successively goes out ethanol, Mierocrystalline cellulose, three kinds of high purity products of composite fertilizer, solve traditional technology and can only extract the drawback of single product, the raw material comprehensive utilization ratio increases substantially, and the effective constituent yield reaches 100%; (2) agent of used xylogen solution-off does not have objectionable constituent such as chlorine, no sulphur, no sodium; (3) there is not the link of contaminate environment in the production process, because the effective constituent of stalk all is extracted out, surplus liquid makes composite fertilizer through acidifying again, whole process of production does not only have traditional technology " three wastes " discharging, also do not have chlorine, no sulphur, no sodium, compare comprehensive pollution indexes with traditional technology and descend 100%; (4) ethanol and cellulosic extraction process are accomplished recycling of water.Compare with traditional technology, the water saving of this technology reaches 90%, meets the industrialization guiding of " recycling economy, saving society ", has very high popularizing value.
Embodiment:
Embodiment 1
1 ton of maize straw, 3 tons of pH values transferred to 3 aqueous sulfuric acid and drop in the stainless steel vessel, under 75 ℃ of temperature, soak reaction 6 hours.The stalk residue is isolated in press filtration then, and filtrate is pressed into fermentation plant, and fractionation by distillation alcohol can be made with extra care 0.15 ton of alcohol; Stalk residue after the press filtration is gone into jar after 2.5 tons water flushing squeezing, and then add 6.5 tons of water, the agent of 20 kilograms of xylogen solution-off, be heated to 85 ℃ the reaction 7 hours, filter coarse product of cellulose, clean bleaching, filter-press dehydration, oven dry, get 0.40 ton of cellulose finished product.Wherein, the solution of flushing is used for the next batch raw material, and the solution of Mierocrystalline cellulose rinsing flows in the stainless steel vessel and utilizes.Surplus liquid after adding the solution behind the sulfuric acid reaction and having extracted Mierocrystalline cellulose concentrates, sprays dried granulation, 0.40 ton of composite fertilizer.
Embodiment 2
1 ton of broomcorn straw, 2.5 tons of pH values transferred to 3 aqueous sulfuric acid and drop in the stainless steel vessel, under 80 ℃ of temperature, soak reaction 6.5 hours.The stalk residue is isolated in press filtration then, and filtrate is pressed into fermentation plant, and fractionation by distillation alcohol can be made with extra care 0.20 ton of alcohol; Stalk residue after the press filtration is gone into jar after 2.5 tons water flushing squeezing, and then add 5 tons of water, the agent of 18 kilograms of xylogen solution-off, be heated to 85 ℃ the reaction 6.5 hours, filter coarse product of cellulose, clean bleaching, filter-press dehydration, oven dry, get 0.35 ton of cellulose finished product.Wherein, the solution of flushing is used for the next batch raw material, and the solution of Mierocrystalline cellulose rinsing flows in the stainless steel vessel and utilizes.Surplus liquid after adding the solution behind the sulfuric acid reaction and having extracted Mierocrystalline cellulose concentrates, sprays dried granulation, 0.38 ton of composite fertilizer.
Claims (6)
1. one kind is the method for raw material co-producing ethanol, Mierocrystalline cellulose, composite fertilizer with the agricultural crop straw, it is characterized in that adopting following steps to realize:
A, will be the agricultural crop straw raw material of coarse crushing and the acidic aqueous solution that the pH value transfers to 2-4 put in the digester by 1 part of mass ratio 2-3 part, being heated to 60-90 ℃ under the normal pressure carried out boiling 4-8 hour;
B, with the reactant after boiling squeezing, the solution that obtains after the squeezing, is adjusted concentration 15-25% at neutralization, zymotechnique is produced ethanol routinely;
The stalk residue that obtains after c, the squeezing washes with the clear water of stalk 2-3 times quality in the relative a step, squeezing the stalk residue that obtains after the flushing again mixes by 1 part of mass ratio to 6-8 part with the aqueous solution that contains the agent of xylogen solution-off, be heated to 60-90 ℃ under the normal pressure and carried out boiling 4-8 hour, filter coarse product of cellulose;
Wherein: the agent of used xylogen solution-off is made of potassiumphosphate 7-8 mass parts, potassium permanganate 1.9-2.9 mass parts, timber permeate agent 0.1 mass parts, and the agent of xylogen solution-off accounts for 0.1-0.5% by quality in the aqueous solution of xylogen solution-off agent;
D, the b step has been extracted the surplus liquid of alcoholic acid and the c step filtered to such an extent that the surplus liquid after the coarse product of cellulose concentrates, sprays dried granulation, made composite fertilizer.
2. according to claim 1 is the method for raw material co-producing ethanol, Mierocrystalline cellulose, composite fertilizer with the agricultural crop straw, it is characterized in that: the acidic aqueous solution in a step is aqueous sulfuric acid or aqueous hydrochloric acid.
3. according to claim 1 is the method for raw material co-producing ethanol, Mierocrystalline cellulose, composite fertilizer with the agricultural crop straw, it is characterized in that: the coarse product of cellulose in the c step promptly gets cellulose finished product through cleaning bleaching, filter-press dehydration, oven dry.
4. according to claim 3 is the method for raw material co-producing ethanol, Mierocrystalline cellulose, composite fertilizer with the agricultural crop straw, it is characterized in that: rinsing liquid is as carrying out needed acidic aqueous solution preparation composition in a step in later batch rinsing liquid or the production process.
5. according to claim 1 is the method for raw material co-producing ethanol, Mierocrystalline cellulose, composite fertilizer with the agricultural crop straw, it is characterized in that: in the c step, the stalk residue is washed with clear water, and the liquid that the squeezing back extrudes is as carrying out needed aqueous sulfuric acid preparation composition in a step in the batch production process later on.
6. according to claim 1 is the method for raw material co-producing ethanol, Mierocrystalline cellulose, composite fertilizer with the agricultural crop straw, it is characterized in that: in a step, the acidic aqueous solution that is used for boiling agricultural crop straw raw material, be the solution that forms behind clear water, last time or cooking liquor several times or the flushing squeezing stalk, in them one or both, three kinds mixed solution, the solution that is deployed into acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910229716A CN101696428A (en) | 2009-10-23 | 2009-10-23 | Method for co-producing ethanol, cellulose and compound fertilizer by using crop straw as raw material |
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| CN200910229716A CN101696428A (en) | 2009-10-23 | 2009-10-23 | Method for co-producing ethanol, cellulose and compound fertilizer by using crop straw as raw material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102533874A (en) * | 2012-02-20 | 2012-07-04 | 任宪君 | Method for producing ethanol by straw solid-liquid double-effect fermentation process |
| CN106011199A (en) * | 2016-07-19 | 2016-10-12 | 南京林业大学 | Method for pre-treating crop straw |
| CN106278400A (en) * | 2016-08-06 | 2017-01-04 | 薛润林 | Culled wood prehydrolysis produces the method for fertilizer |
| CN107177646A (en) * | 2017-06-16 | 2017-09-19 | 中南大学 | A kind of method of utilization lignin-degrading bacteria reinforcing abandoned biomass acid system pretreatment |
| CN107558284A (en) * | 2017-08-31 | 2018-01-09 | 南京工业大学 | A kind of method that lignin co-production phosphorus potassium complex fertilizer is extracted using fermenting cellulosic ethanol residue as raw material |
| CN117682927A (en) * | 2024-02-04 | 2024-03-12 | 四川大学 | Polypeptide compound fertilizer and preparation method of polypeptide compound fertilizer and microcrystalline cellulose |
-
2009
- 2009-10-23 CN CN200910229716A patent/CN101696428A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102533874A (en) * | 2012-02-20 | 2012-07-04 | 任宪君 | Method for producing ethanol by straw solid-liquid double-effect fermentation process |
| CN106011199A (en) * | 2016-07-19 | 2016-10-12 | 南京林业大学 | Method for pre-treating crop straw |
| CN106011199B (en) * | 2016-07-19 | 2020-01-10 | 南京林业大学 | Pretreatment method of crop straws |
| CN106278400A (en) * | 2016-08-06 | 2017-01-04 | 薛润林 | Culled wood prehydrolysis produces the method for fertilizer |
| CN107177646A (en) * | 2017-06-16 | 2017-09-19 | 中南大学 | A kind of method of utilization lignin-degrading bacteria reinforcing abandoned biomass acid system pretreatment |
| CN107177646B (en) * | 2017-06-16 | 2020-11-17 | 中南大学 | Method for strengthening acid pretreatment of waste biomass by using lignin-degrading bacteria |
| CN107558284A (en) * | 2017-08-31 | 2018-01-09 | 南京工业大学 | A kind of method that lignin co-production phosphorus potassium complex fertilizer is extracted using fermenting cellulosic ethanol residue as raw material |
| CN117682927A (en) * | 2024-02-04 | 2024-03-12 | 四川大学 | Polypeptide compound fertilizer and preparation method of polypeptide compound fertilizer and microcrystalline cellulose |
| CN117682927B (en) * | 2024-02-04 | 2024-04-16 | 四川大学 | Polypeptide compound fertilizer and preparation method of polypeptide compound fertilizer and microcrystalline cellulose |
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Open date: 20100421 |