CN108611897A - A method of extraction fruits and vegetables residue prepares levelling agent - Google Patents
A method of extraction fruits and vegetables residue prepares levelling agent Download PDFInfo
- Publication number
- CN108611897A CN108611897A CN201810616622.5A CN201810616622A CN108611897A CN 108611897 A CN108611897 A CN 108611897A CN 201810616622 A CN201810616622 A CN 201810616622A CN 108611897 A CN108611897 A CN 108611897A
- Authority
- CN
- China
- Prior art keywords
- cellulose
- extraction
- eutectic solvent
- levelling agent
- residue
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/02—Rendering cellulose suitable for esterification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
- C08B3/18—Aceto-butyrates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/47—Levelling agents
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Wood Science & Technology (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The present invention relates to a kind of methods preparing levelling agent using cellulose in the fruit trees residues such as eutectic solvent extraction Grape Skin, grape pip, citrus, including the technique for selecting alkaline eutectic solvent extraction cellulose and acid eutectic solvent to participate in cellulose esterification.The physicochemical properties of eutectic solvent are adjusted by selecting suitable composition and proportioning, its application power as green solvent in cellulose extracts esterification process is played, realizes the friendly process for preparing cellulose ester-based levelling agent using different fruits and vegetables residues.
Description
Technical field
Fruits and vegetables are residual under being participated in the present invention relates to a kind of method that extraction fruits and vegetables residue prepares levelling agent, including eutectic solvent
The extraction of cellulose in slag, cellulose esterification technique, belong to the pretreatment of cellulose and the preparation field of cellulose esters.
Background technology
It is the key factor for influencing agricultural development that agricultural wastes recycling, which recycles, is national development biomass energy
Key strategy, it can be achieved that agricultural wastes become " useless " as " treasured ", improve the ecological environment by elimination environmental pollution, promote it is agriculture can
Sustainable development.2016, country put into effect《About the scheme for promoting agricultural wastes recycling pilot》, clearly dispose and enclose
It around agricultural crop straw the like waste, is served as theme with on-site elimination, energy circulation, comprehensive utilization, puts forth effort to explore structure agriculture waste
Effective governance model that object recycling recycles.It is counted according to State Statistics Bureau, the Ministry of Agriculture, China's fruits and vegetables total output is about within 2016
10.5 hundred million tons, about generate 2.9 hundred million tons of fruit/vegetable waste.Fruit/vegetable waste can be by extracting polyphenol, protein, amino acid, fruit
Glue etc. is utilized, and the residue after extraction contains the ingredients such as a large amount of celluloses, hemicellulose and lignin, and generally use is directly covered
It buries or burns, not only result in waste of resources, but also pollute environment, it has also become the problem of can not be ignored.Therefore, how residual to fruits and vegetables
Slag carries out recycling recycling, improves its added value, is the critical issue of garden stuff processing industry urgent need to resolve.
Currently, the use aspects in fruits and vegetables residue mainly use the conventional methods such as ensiling, fermentation, carbonization, it is translated into
The products such as animal feed, organic fertilizer, biomass carbon.However, the prior art has been difficult to adapt to the demand of Vehicles Collected from Market economy, exist
Fruits and vegetables residue is using backward in technique, and utilization rate is low, and promotional value is not high.Such as the waste after pineapple deep processing, baking is mostly used greatly
The mode of direct combustion heat supplying or returning to the field is done, innovative technique is few；The residues such as apple, citrus can be made into animal feed, realize
Resource reutilization to a certain extent, but the problems such as added value is low, and there are agriculture chemical residuals.It is produced with cellulose esterification high attached
For value added cellulose esters, the basic unit in fruits and vegetables residue with the lignin deposited is phenylpropyl alcohol alkyl, by ehter bond and carbon-carbon bond chain
It connects, not only itself can not be hydrolyzed, and form protective layer around cellulose and hemicellulose, influence cellulose and half fiber
Tie up the esterification of element.
Cellulose is cheap, nontoxic, biodegradable, and application pushes away Chen Zhixin, and the extraction of cellulose is still
It is the hot and difficult issue studied both at home and abroad.Currently, physical method causes cellulose degradation serious in the extracting method of cellulose, acid
Alkali process method generates a large amount of waste liquids, and organic solvent system for handling can realize solvent recovery, but will also result in volatile organic
Close object（VOC）Pollution.Ionic liquid can efficiently separate cellulose, but its cost is higher, it is difficult to form industrialization.It is emerging " low
Congruent melting solvent " technology abandons mechanical lapping and chemical steaming, can be purified during residue treatment cellulose and can by-product it is high-purity
Lignin.In addition, its dispersion and swellability can be significantly increased to cellulosic material pretreatment using DES, in carrying for cellulose
It takes and shows greater advantage in conversion process.Change DES hydrogen bond donor and receptor type and content, it can be achieved that lignin,
The orientation of cellulose is extracted, and partially acidic DES can prepare high added value Cellulose nanocrystal, and DES can also be directly as reaction
Solvent realizes that cellulose is controllable modified.However, the holes main body DES capture the specificity of object cellulose, lignin, Subjective and Objective
The extractions such as the mode of action and action intensity conversion in general character and individual character the problems such as need further to be probed into.
Levelling agent is a kind of important coating additive, and coating can be assigned during drying and forming-film and forms a smooth, light
Sliding, uniform film.Used powder coating leveling agent has both at home and abroad at present：Cellaburate, gathers polyvinyl butyral
Acrylate, modified polyacrylate etc..It is generated with the three wastes during chemical modification for the extraction of current fruits and vegetables residue cellulose
Seriously, the problems such as added value of product is low, the present invention improve cellulose extraction process using eutectic solvent technology, realize mild item
Under part in fruits and vegetables residue cellulose high efficiency extraction, establish cellulose green esterification conversion key technology system, break through existing work
The bottleneck problem that the high spent acid of skill generates, utilizes for industrialization and lays the foundation.
Invention content
Patent of the present invention is designed to provide a kind of method that extraction fruits and vegetables residue prepares levelling agent.
In order to achieve the above objectives, specific technical solution of the present invention is：
（1）Cellulose in fruit tree residue is extracted using eutectic solvent, extraction system includes：Fruit tree residue, eutectic solvent,
In, in mass ratio, the ﹕ 1 ~ 20 of fruit tree residue, eutectic solvent=1；Extracting temperature：20 ~ 60 degrees Celsius；Extraction time：1 ~ 3 time；
Extraction time：6 ~ 24 hours；
Wherein, the fruit tree residue is：One kind in Grape Skin, grape pip, apple pericarp, orange peel, banana skin, pomelo peel；
The eutectic solvent is：One kind in choline chloride/urea, tetrabutylammonium hydroxide/dimethyl sulfoxide.
（2）Utilize step（1）The cellulose of extraction carries out esterification and prepares levelling agent, and esterification system includes step
（1）Cellulose, n-butyric acie, acetic anhydride, the eutectic solvent of extraction, wherein in mass ratio, cellulose, unsaturated fatty acid, low total
Molten solvent=100 ~ 500 ﹕, 0 ~ 500 ﹕, 0 ~ 100 ﹕ 20 ~ 200：100~1000；Esterification reaction temperature：60 ~ 80 degrees Celsius；When reaction
Between：1 ~ 4 hour；It pours into after reaction in a large amount of water and fully washs, filters, drying and prepare cellulose base levelling agent；
Wherein, the cellulose is：Step（1）The cellulose of extraction；
The eutectic solvent is：One kind in choline chloride/malonic acid, choline chloride/oxalic acid, choline chloride/ethylene glycol.
Above-mentioned reaction system provide it is a kind of using extraction fruits and vegetables residue prepare levelling agent method.Therefore, the present invention claims
It protects simultaneously and synthesizes levelling agent, including following aspect using above-mentioned reaction system：
（1）The extraction of cellulose in the lower fruits and vegetables residue of eutectic solvent effect；
（2）The esterification technique of cellulose in the lower fruits and vegetables residue extracted of eutectic solvent effect；
（3）The flow leveling of the cellulose ester-based levelling agent of synthesis.
Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
（1）The present invention prepares the fruits such as Grape Skin, grape pip, apple pericarp, orange peel, banana skin, the pomelo peel that levelling agent utilizes
On the one hand vegetable residue solves fruits and vegetables residue waste pollution environmental problem, the levelling agent cost on the other hand prepared is relatively low, adds
Value is higher；
（2）The present invention prepares the extraction and esterification that levelling agent realizes cellulose in fruit tree residue using the eutectic solvent of low cost
The problems such as process has the characteristics that stronger green, environmental protection, effectively eliminated shrinkage cavity, the tangerine peel of coating, improves the stream of coating
Levelling energy.
Specific implementation mode
With reference to exemplary embodiments, the invention will be further described, but the present invention is not limited to following implementation cases
Example.The method is conventional method unless otherwise specified.The raw material unless otherwise instructed can be from open commercial sources
And it obtains.Chemical reagent used：Choline chloride analyzes pure Sinopharm Chemical Reagent Co., Ltd.；The pure Chinese medicines group of Analysis of Urea
Chemical reagent Co., Ltd；Tetrabutylammonium hydroxide analyzes pure Sinopharm Chemical Reagent Co., Ltd.；Dimethyl sulfoxide analysis is pure
Sinopharm Chemical Reagent Co., Ltd.；N-butyric acie analyzes pure Sinopharm Chemical Reagent Co., Ltd.；Acetic anhydride analyzes pure traditional Chinese medicines
Chemical reagent Co., Ltd of group；Choline chloride/malonic acid analyzes pure Sinopharm Chemical Reagent Co., Ltd.；Oxalic acid analysis is pure
Sinopharm Chemical Reagent Co., Ltd.；Ethylene glycol analyzes pure Sinopharm Chemical Reagent Co., Ltd.；Tetrahydrofuran analysis is pure
Sinopharm Chemical Reagent Co., Ltd..
Embodiment one：The extraction process of cellulose
By citrus residue after solarization, it is cut into 3-5 centimetres of small item, is milled to powder, between being used in combination sieve to filter out 60-80 mesh
Powder.1000 grams of citrus residue powder is added in the eutectic solvent of 2000 milliliters of choline chloride/ureas, under mechanical agitation
It is heated to 50 degrees Celsius, after reaction 10 hours, filtering drying is repeated 2 times, and is washed with deionized and is dried to obtain citrus residue and carries
860 grams of cellulose after taking.
Embodiment two：The esterification technique of cellulose
100 grams of the cellulose that will be obtained in case study on implementation one is taken, the eutectic that 250 milliliters of choline chloride/ethylene glycol is added is molten
20 milliliters of n-butyric acie, 20 milliliters of acetic anhydride are added dropwise in agent, under mechanical agitation, is added dropwise after 30 minutes, is warming up to 80
Degree Celsius reaction 2 hours, pours into 90 grams of cellulose esters is fully washed, filters, be dried to obtain in a large amount of water after reaction.
Embodiment three：The characterization of cellulose esters structural behaviour
10 milligrams of cellulose esters prepared by case study on implementation two is taken to be dissolved in 5 milliliters of tetrahydrofuran solution, it is poly- using ultra high efficiency
Spectrum is looked in conjunction（APC）, polystyrene is standard specimen, its number-average molecular weight 3.5 ten thousand or so of survey, molecular weight distribution 1.8；Take implementation
It is 2.2s/pa that 100 milligrams of cellulose esters prepared by case two, which selects its viscosity of rotational rheometer,.Nucleus magnetic hydrogen spectrum shows its second
Acyl group content 14.8%, bytyry content is 38.3%, and hydroxy radical content is 1.5% or so.DSC tests show that its fusing point is taken the photograph for 198.6
Family name's degree, glass transition temperature are 135.2 degrees Celsius.It is imitated with preferable levelling as coating additive as additive
Fruit, no shrinkage cavity occur.
Claims (2)
1. a kind of method that extraction fruits and vegetables residue prepares levelling agent, including following 2 steps, it is characterised in that：
（1）Cellulose in fruit tree residue is extracted using eutectic solvent, extraction system includes：Fruit tree residue, eutectic solvent,
In, in mass ratio, the ﹕ 1 ~ 20 of fruit tree residue, eutectic solvent=1；Extracting temperature：20 ~ 60 degrees Celsius；Extraction time：1 ~ 3 time；
Extraction time：6 ~ 24 hours；
Wherein, the fruit tree residue is：One kind in Grape Skin, grape pip, apple pericarp, orange peel, banana skin, pomelo peel；
The eutectic solvent is：One kind in choline chloride/urea, tetrabutylammonium hydroxide/dimethyl sulfoxide；
（2）Utilize step（1）The cellulose of extraction carries out esterification and prepares levelling agent, and esterification system includes step（1）
Cellulose, n-butyric acie, acetic anhydride, the eutectic solvent of extraction, wherein in mass ratio, cellulose, unsaturated fatty acid, eutectic
Solvent=100 ~ 500 ﹕, 0 ~ 500 ﹕, 0 ~ 100 ﹕ 20 ~ 200：100~1000；Esterification reaction temperature：60 ~ 80 degrees Celsius；Reaction time：1
~ 4 hours；It pours into after reaction in a large amount of water and fully washs, filters, drying and prepare cellulose base levelling agent；
Wherein, the cellulose is：Step（1）The cellulose of extraction；
The eutectic solvent is：One kind in choline chloride/malonic acid, choline chloride/oxalic acid, choline chloride/ethylene glycol.
2. a kind of extracting the levelling agent prepared by esterification technique after cellulose by described in claim 1 by fruits and vegetables residue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810616622.5A CN108611897A (en) | 2018-06-15 | 2018-06-15 | A method of extraction fruits and vegetables residue prepares levelling agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810616622.5A CN108611897A (en) | 2018-06-15 | 2018-06-15 | A method of extraction fruits and vegetables residue prepares levelling agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108611897A true CN108611897A (en) | 2018-10-02 |
Family
ID=63665144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810616622.5A Pending CN108611897A (en) | 2018-06-15 | 2018-06-15 | A method of extraction fruits and vegetables residue prepares levelling agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108611897A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110668506A (en) * | 2019-09-29 | 2020-01-10 | 昆明理工大学 | Method for recycling and regenerating lithium cobaltate from waste lithium ion battery |
| CN112175095A (en) * | 2020-10-30 | 2021-01-05 | 齐鲁工业大学 | Method for sulfonating modified cellulose by ternary eutectic solvent system |
| CN113578289A (en) * | 2021-08-05 | 2021-11-02 | 河北科技大学 | Eutectic solvent, carbon quantum dot-loaded porous adsorbent, and preparation method and application thereof |
| IT202000012019A1 (en) * | 2020-05-22 | 2021-11-22 | Milano Politecnico | PROCESS FOR THE TREATMENT OF BIOMASS CONSISTING OF CITRUS PASTA |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100285553A1 (en) * | 2008-01-25 | 2010-11-11 | Compagnie Industrielle De La Matiere Vegetale Cimv | Process for pretreating a lignocellulosic material with a view to producing bioethanol, and bioethanol production process |
| CN104887723A (en) * | 2015-06-18 | 2015-09-09 | 天津理工大学 | Method for extracting flavonoids from ginkgo biloba leaves with deep eutectic solvent |
| CN106518590A (en) * | 2016-09-18 | 2017-03-22 | 曲阜师范大学 | Method for extracting polyphenol substances from pomegranate peel by using low eutectic solvent |
| CN107936072A (en) * | 2017-12-12 | 2018-04-20 | 江苏省农业科学院 | A kind of method using eutectic solvent extraction blackberry anthocyanin |
| CN108048421A (en) * | 2017-12-14 | 2018-05-18 | 天津科技大学 | The method that transfructosylase catalytic efficiency and stability are improved using choline eutectic solvent |
-
2018
- 2018-06-15 CN CN201810616622.5A patent/CN108611897A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100285553A1 (en) * | 2008-01-25 | 2010-11-11 | Compagnie Industrielle De La Matiere Vegetale Cimv | Process for pretreating a lignocellulosic material with a view to producing bioethanol, and bioethanol production process |
| CN104887723A (en) * | 2015-06-18 | 2015-09-09 | 天津理工大学 | Method for extracting flavonoids from ginkgo biloba leaves with deep eutectic solvent |
| CN106518590A (en) * | 2016-09-18 | 2017-03-22 | 曲阜师范大学 | Method for extracting polyphenol substances from pomegranate peel by using low eutectic solvent |
| CN107936072A (en) * | 2017-12-12 | 2018-04-20 | 江苏省农业科学院 | A kind of method using eutectic solvent extraction blackberry anthocyanin |
| CN108048421A (en) * | 2017-12-14 | 2018-05-18 | 天津科技大学 | The method that transfructosylase catalytic efficiency and stability are improved using choline eutectic solvent |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110668506A (en) * | 2019-09-29 | 2020-01-10 | 昆明理工大学 | Method for recycling and regenerating lithium cobaltate from waste lithium ion battery |
| IT202000012019A1 (en) * | 2020-05-22 | 2021-11-22 | Milano Politecnico | PROCESS FOR THE TREATMENT OF BIOMASS CONSISTING OF CITRUS PASTA |
| WO2021234620A1 (en) * | 2020-05-22 | 2021-11-25 | Politecnico Di Milano | Process for treating biomass consisting of citrus pastazzo |
| CN112175095A (en) * | 2020-10-30 | 2021-01-05 | 齐鲁工业大学 | Method for sulfonating modified cellulose by ternary eutectic solvent system |
| CN113578289A (en) * | 2021-08-05 | 2021-11-02 | 河北科技大学 | Eutectic solvent, carbon quantum dot-loaded porous adsorbent, and preparation method and application thereof |
| CN113578289B (en) * | 2021-08-05 | 2023-04-11 | 河北科技大学 | Eutectic solvent, carbon quantum dot-loaded porous adsorbent, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108611897A (en) | A method of extraction fruits and vegetables residue prepares levelling agent | |
| CN102085680B (en) | Preparation method of crop straw fiber ecological composite material | |
| CN102212375B (en) | Preparation method of machine-made charcoal and machine-made charcoal | |
| Yasim-Anuar et al. | Factors Affecting Spinnability of Oil Palm Mesocarp Fiber Cellulose Solution for the Production of Microfiber. | |
| CN110978171B (en) | Preparation method and application of bamboo pulp fiber and bamboo extract from bamboo | |
| CN105399872B (en) | A kind of method and application using Jujun grasses Preparation of Activated Carbon with Lignin | |
| CN105316366A (en) | Production method for comprehensively utilizing biological straw | |
| CN104479369B (en) | A kind of degradation plastic containing algae albumen and preparation method thereof | |
| CN102061314B (en) | Method for coproducing methane and solid formed fuel by using herbaceous wood fiber as raw material | |
| CN104130034A (en) | Method for producing fiber board and organic fertilizer by utilizing garden waste | |
| CN104629902A (en) | Method for extracting maize germ oil assisted by ethyl alcohol and steam explosion | |
| CN105297511A (en) | Separation method of organic constituent in agricultural waste | |
| CN105000981A (en) | Carbonized particle fermented organic fertilizer and preparation method therefor | |
| CN109112891A (en) | A method of wrapping paper is prepared with arghan and banana caulo slurry | |
| CN106832591A (en) | A kind of biomass composite of oil-tea camellia husks base and preparation method thereof | |
| CN106520154A (en) | Processing method of husk slag of Xanthoceras sorbifolia Bunge and products | |
| CN103666622A (en) | Preparation method of mulberry twig granular biofuel | |
| CN106418322B (en) | A kind of method of soluble dietary fibre content in raising apple pomace | |
| CN105462287B (en) | A kind of extracting method of lavender dyestuff and its application in regenerated celulose fibre dyeing | |
| CN101463571A (en) | Pretreatment method for ultra-high pressure blasting wood fiber material | |
| JP2009213449A (en) | Method for producing monosaccharide and ethanol by using oil-based plant biomass residue as raw material | |
| CN105037747A (en) | Method for extracting fulvic acid from fermented products of kitchen waste | |
| CN102180724A (en) | Preparation method for light soilless culture substrate material | |
| CN208104290U (en) | Biomass castoff processing system | |
| CN105968227A (en) | Process of extracting pectin from snake gourd peel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181002 |