CN102733223B - Pulping method by catalysis of low boiling point solvent with diluted acid generated from xylose residue and furfural residue - Google Patents
Pulping method by catalysis of low boiling point solvent with diluted acid generated from xylose residue and furfural residue Download PDFInfo
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- CN102733223B CN102733223B CN201210201392.9A CN201210201392A CN102733223B CN 102733223 B CN102733223 B CN 102733223B CN 201210201392 A CN201210201392 A CN 201210201392A CN 102733223 B CN102733223 B CN 102733223B
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Abstract
The present invention provides a pulping method by catalysis of a low boiling point solvent with a diluted acid generated from xylose residue and furfural residue. According to the method, acid solid wastes generated from xylose production and furfural production are adopted as raw materials, the residual acid in the xylose residue and the furfural residue is adopted as a catalyst, a solvent is adopted as a pulping solvent, a low temperature and a short reaction time are adopted to carry out pulping, and steps of steaming boiling, filtering, washing, distilling, filtering, and the like are performed to achieve pulping by catalysis of the low boiling point solvent with the diluted acid generated from the xylose residue and the furfural residue, wherein the boiling point of the solvent is less than 100 DEG, or the solvent and water can form an azeotrope with the boiling point less than 100 DEG C. The solvent used for pulping can be recovered by distillation, and the extracted lignin can be used as a substitute of a phenol formaldehyde adhesive in plywood. The method of the present invention has advantages of reasonable and practicable process, easy operation, low pollution, low pulping cost, high pulping yield, and the like.
Description
Technical field
The present invention relates to pulp technology for making paper, particularly relate to a kind of xylose residue and furfural dregs diluted acid catalysis low boiling point solvent pulping process.
Technical background
Xylose residue, furfural dregs utilize corncob to make raw material, and produce the acid solid discarded object after wood sugar, furfural, its main component is cellulose and lignin.Xylose residue, furfural dregs are a kind of lignocellulosic sources of high-quality, and content of cellulose is more than 50%.Lignocellulose is the regenerative resource of the most potentiality that the earth accumulates.How reasonably this resource of exploitation, has been a great concern in the world, to its utilization in the world multiple country dropped into a large amount of funds and studied.In recent years, the research around biomass economy focuses mostly in materials such as maize straw, rice straw and pine sawdusts, and less to ligno-cellulosic materials researchs such as sugaring and furfural residues.Xylose residue and furfural dregs are in process of production through acid hydrolysis preliminary treatment, and therefore it more easily utilizes.Along with the fast development of economy, the quantity of production wood sugar, furfural enterprise gets more and more, and production scale is increasing, and the discharge capacity of xylose residue, furfural dregs also increases year by year.Generally, produce more than 10 tons, the waste residue of 1 ton of crystalline xylose or furfural discharge moisture 70 ~ 80%, discharge nearly 5,000,000 tons of xylose residue, furfural dregs at present every year.The air storage of waste residue not only occupies a large amount of arable lands, and causes severe contamination to surrounding enviroment.Strong wind blows afloat waste residue, causes atmosphere pollution; Rain drop erosion waste residue flows into farmland, causes the pollution of soil; Permeate the ground, enter river, cause water pollution.Reasonably development and utilization castaway slag, can not only Control pollution, and protect the fields ecological environment, also can obtain significant economic benefit.These castaway slag Land use systems roughly have following several at present: directly burning compression forming charcoal processing, employing heat chemistry mode are converted into gas or liquid fuel, anaerobic fermentation Biogas, produce bio-organic fertilizer, culturing edible fungus, making fiberboard and careless plate, prepare chemicals levulic acid and lignin active carbon etc.
Because these castaway slags contain higher cellulose, it is also a kind of pulping raw material preferably.Xylose residue and furfural dregs pulping process is utilized to study less at present.
Current paper industry is with sulfate pulping, soda pulping for main flow, and the major defect of this class methods slurrying is seriously polluted, and investment cost is high.People have developed organic solvent pulping in recent years, and achieve certain achievement.Organosolv pulping revolutionizes the situation that traditional pulping process depends on alkali or acid, organic solvent in organic solvent pulping comprises alcohols (methyl alcohol, ethanol, butanols), sough in acids (formic acid, acetic acid), ethers (ether), ester class, phenols, diformazan Asia, the dissolubility utilizing it good and effumability, by be separated, hydrolysis, dissolve or and lignin generation chemical reaction, reach lignin to be efficiently separated with cellulosic, thus reach the object of slurrying.Wherein ethanol be study the most up to now, the most ripe slurrying solvent.Compared with other solvent pulpings, the delignification stages of Ethanol Method in digestion process does not need to add any auxiliary agent or catalyst.Ethanol pulping is applicable to the production of small-scale, and cost is lower, has no significant effect environment, and its byproduct has very large potential commercial value.Compared with traditional sulfate pulp, Ethanol Method slurry has following characteristics: opacity is high, YI yellow index is low, dirt count is low, extract content is low, wet strength is high, fines content is low.In slurrying, ethanol can adopt simple method to recycle, and the structure of its accessory substance lignin does not have larger change, can obtain a lot of new product, brings significant social benefit and environmental benefit.
Organic solvent pulping is divided into self-catalysis, base catalysis and acid catalysis.Wherein when self-catalysis and base catalysis, the pH value of cooking liquor is higher, the stripping of institute's silicon oxide-containing in fibrous raw material can not be stoped, cause there is silicon obstacle problem in the subsequent treatment of boiling raffinate, and xylose residue and furfural dregs self-catalysis or base catalysis will be realized, need the acid removed contained by xylose residue and furfural dregs and bring the consumption of extra alkali thus increase process costs, also making complex process, the capacity usage ratio in pulping process is low, chemicals heavily reuses more difficult.The acid catalysis organosolv pulping utilizing xylose residue and furfural dregs to bring in process of production can reduce delignification reaction temperature, Reaction time shorten, is conducive to reducing process energy consumption.
High boiling solvent (hbs) slurrying uses high boiling alcohols to do organic solvent to carry out boiling dissolved lignin, obtain and be used for height that the fiber of papermaking and lignin mainly use the at present alcohol that boils and have butanediol, propylene glycol, ethylene glycol, pentanediol and tetrahydrofurfuryl alcohol, polyethylene glycol, polypropylene glycol etc., but height boils, alcohol is higher due to boiling point, reclaims energy consumption higher.
Summary of the invention
The object of the invention is, for the utilization of xylose residue and furfural dregs provides a new processing technology routine, to provide a kind of xylose residue and furfural dregs diluted acid catalysis low boiling point solvent pulping process.
The present invention utilizes acid remaining in xylose residue, furfural dregs to be catalyst, boiling point is selected to be less than 100 DEG C or the boiling point of azeotropic mixture that formed with water is less than the solvent (as methyl alcohol, ethanol, acetone or butanols etc.) of 100 DEG C as slurrying solvent, xylose residue and furfural dregs are under the catalytic action of diluted acid, under lower temperature with pressure by being separated, boiling, dissolving or lignin is separated with lignin generation chemical reaction with cellulose, prepare slurry.
The inventive method specifically comprises the steps:
1) xylose residue and furfural dregs are added in the reactor with cooling coil, be 4 ~ 14 low boiling point solvent aqueous solution adding that volume ratio is 35 ~ 65% by solid-to-liquid ratio, after being heated to 140 ~ 200 DEG C, cooking reaction is after 0.5 ~ 2.5 hour, cooling water is passed in cooling coil, cool to rapidly 40 ~ 90 DEG C, discharge product;
2) collecting reaction product, filters, obtains filtrate and filter residue;
3) add temperature in filter residue to be 40 ~ 90 DEG C, be 2 ~ 10 by solid-to-liquid ratio to be 35 ~ 65% low boiling point solvent solution washings by volume ratio, filter, collect filtrate and filter residue, this filter residue is product coarse slurry;
4) by the filtrate of reaction and wash filtrate mixing, adopt normal pressure or decompression distillation mode recycling design, carry out filtration to vinasse and obtain filtrate and filter residue, this filter residue is the lignin of the byproduct-purification of slurrying.
In described step (1), described low boiling point solvent is the organic solvent that its boiling point or the boiling point of azeotropic mixture that formed with water are less than 100 DEG C, as methyl alcohol, ethanol, acetone and butanols etc., different low boiling point solvents can arbitrary proportion used in combination.
In described step (3), washing can be carried out repeatedly.
In described step (4), the filtrate after recycling design can send into sewage treatment plant's process.
The thick slurry obtained in step (3) may be used for the preparation of bleach chemical pulp.The byproduct purifying lignin obtained in step (4) can be used for the substitute of adhesive in phenolic aldehyde formaldehyde adhesive in shaving board, glued board and rubber production.
The pluses and minuses of the comprehensive existing solvent pulping technology of the present invention, adopt low boiling point solvent, with xylose residue, furfural dregs for raw material, acid remaining in xylose residue, furfural dregs is utilized to be catalyst, adopt lower temperature and shorter reaction time slurrying, low boiling point solvent, by Distillation recovery, also obtains the lignin of higher degree simultaneously, whole technique environmental protection, the energy consumption of pulping process is lower.The invention has the advantages that:
(1) choose the byproduct xylose residue producing wood sugar and furfural and furfural dregs as raw material, raw materials for production are easy to obtain, and slurrying is with low cost.
(2) production Technology clean environment firendly, the solvent recoverable used in slurrying, reduces discharging of waste liquid amount.
(3) can obtain the byproducts such as high Vinsol while slurrying, alternative adhesive, obtains higher value application.
(4) pulping process is simple, easy and simple to handle, is easy to industry's enlarging production.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1: xylose residue slurrying
According to technological parameter shown in table 1, corncob will be utilized to make raw material, and produce the reactor that cooling coil is equipped with in inside that the xylose residue after wood sugar drops into 5 liters, add ethanol water, carry out delignification's cooking reaction under certain temperature and pressure.Pass into cooling water and be cooled to rapidly 40 ~ 90 DEG C after reaction certain hour, filter product, be 2 ~ 10 with ethanol water washing filter residue twice by solid-to-liquid ratio after filtration, filter, filter residue is cellulose coarse particles prepared by xylose residue; After filtered fluid and cleaning solution mix, by steaming ethanol, filtered by remaining raffinate, filter residue is the lignin of purification, can as the raw material of other products.Result of the test is in table 1.
Table 1 experimental technique condition
Embodiment 2: furfural dregs slurrying
According to technological parameter shown in table 2, corncob will be utilized to make raw material, and produce the reactor that cooling coil is equipped with in inside that the furfural dregs after furfural drops into 5 liters, add solvent aqueous solution, carry out delignification's cooking reaction in certain temperature under high and pressure.Pass into cooling water and be cooled to rapidly 40 ~ 90 DEG C after reaction certain hour, filter product, be 2 ~ 10 wash filter residue with solvent aqueous solution by solid-to-liquid ratio after filtration, filter, filter residue is cellulose coarse particles prepared by furfural dregs; After filtered fluid and cleaning solution mix, by steaming solvent, filtered by remaining raffinate, filter residue is the lignin of purification, can as the raw material of other products.
Table 2 experimental technique condition
Claims (1)
1. xylose residue and a furfural dregs diluted acid catalysis low boiling point solvent pulping process, is characterized in that, comprise the steps:
1) xylose residue and furfural dregs are added in the reactor with cooling coil, be 4 ~ 14 low boiling point solvent aqueous solution adding that volume ratio is 35 ~ 65% by solid-to-liquid ratio, acid remaining in xylose residue, furfural dregs is utilized to be catalyst, after being heated to 140 ~ 200 DEG C, cooking reaction is after 0.5 ~ 2.5 hour, cooling water is passed in cooling coil, cool to rapidly 40 ~ 90 DEG C, discharge product; Described low boiling point solvent be selected from methyl alcohol, ethanol, acetone or butanols one or more mixing, different low boiling point solvents can arbitrary proportion used in combination;
2) collecting reaction product, filters, obtains filtrate and filter residue;
3) add temperature in filter residue to be 40 ~ 90 DEG C, be 2 ~ 10 by solid-to-liquid ratio to be the low boiling point solvent solution washing of 35 ~ 65% by volume ratio, filter, collect filtrate and thick slurry;
4) by the filtrate of reaction and cleaning solution mixing, adopt normal pressure or decompression distillation mode recycling design, filtration is carried out to vinasse and obtains filtrate and filter residue, the lignin that the byproduct that filter residue is slurrying is purified.
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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 |
| CN107129848A (en) * | 2017-04-21 | 2017-09-05 | 常州思宇环保材料科技有限公司 | A kind of preparation method of complex biological matter briquette binder |
| CN109778582A (en) * | 2017-11-13 | 2019-05-21 | 中国科学院大连化学物理研究所 | The method of cellulose, hemicellulose and lignin in solvent-thermal method separating biomass |
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| US5730837A (en) * | 1994-12-02 | 1998-03-24 | Midwest Research Institute | Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars |
| CN1566520A (en) * | 2003-07-03 | 2005-01-19 | 陕西科技大学 | Pulping process by acid catalyzed ethanol method |
| CN101215795A (en) * | 2008-01-09 | 2008-07-09 | 天津科技大学 | Sulfuric acid catalysis ethanol pulp preparing technique for ryegrass |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5730837A (en) * | 1994-12-02 | 1998-03-24 | Midwest Research Institute | Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars |
| CN1566520A (en) * | 2003-07-03 | 2005-01-19 | 陕西科技大学 | Pulping process by acid catalyzed ethanol method |
| CN101215795A (en) * | 2008-01-09 | 2008-07-09 | 天津科技大学 | Sulfuric acid catalysis ethanol pulp preparing technique for ryegrass |
Non-Patent Citations (2)
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| 糠醛渣制浆配抄瓦楞原纸;秦知子;《纸和造纸》;19910531(第2期);53-54 * |
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