CN107417930B - A kind of biomass acid material and preparation method thereof - Google Patents

A kind of biomass acid material and preparation method thereof Download PDF

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Publication number
CN107417930B
CN107417930B CN201710480372.2A CN201710480372A CN107417930B CN 107417930 B CN107417930 B CN 107417930B CN 201710480372 A CN201710480372 A CN 201710480372A CN 107417930 B CN107417930 B CN 107417930B
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acid
biomass
formylsalicylic
powder
biological material
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CN107417930A (en
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孟庆华
朱虹
李忠
李建红
程道远
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Nanjing Han flag new material Limited by Share Ltd
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Nanjing Han Qi Novel Material Science And Technology Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08HDERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00Macromolecular compounds derived from lignocellulosic materials

Abstract

The invention discloses a kind of biomass acid materials, it is obtained after being reacted by biological material with formylsalicylic acid, wherein the biological material contains one or more of active group hydroxyl, amino, aldehyde radical or ester group.Biomass acid material of the present invention, what is utilized is the leftover pieces of natural plant resource, does not need additionally to increase resource consumption, meets recycling economy requirement.

Description

A kind of biomass acid material and preparation method thereof
Technical field
The invention belongs to natural products and circular economy field, and in particular to a kind of modified preparation of biomass acid material.
Background technique
Biological material is using xylophyta, gramineae plant and liana and its industrial wood waste and waste as former material Material, by the high technological means such as physics, chemistry and biology, processing and manufacturing had excellent performance, the new material that added value is high.
Coconut husk (latin name:Cocos Nucifera L.) be babassu coconut endocarp, it is dry after cutin thin slice Shape, brown brown, matter are extremely hard.Chemical component coconut husk contains ash content 0.61%, lignin 36.51%, cellulose 53.06%, pentosan 29.27% (total amount).
The powder that timber is broken into generally refers to Furniture Factory, density board factory, the remaining side of multi-layer board factory timber processing wood powder Horn scraps.Main component are as follows: cellulose 41%, hemicellulose 31%, lignin 29%.
Bamboo powder raw material is also very abundant, processes remaining leftover pieces using bamboo, broken cutting, drying sterilizing, crushing are ground Mill, drying sterilizing are at powder.
Stalk is the general name of mature crops cauline leaf (fringe) part.It is often referred to wheat, rice, corn, potato, rape, cotton Flower, the remainder of sugarcane and other crops (usually coarse food grain) after harvesting seed.The photosynthetic product of crops has More than half is present in stalk, and stalk is rich in organic matter, is a kind of with multiduty reproducible living resources, crude fibre Content height (30%-40%), and contain lignin etc..
Contain hydroxyl structure abundant in these substances, amino, aldehyde radical or ester group, Ke Yili are generated when some kinds or processing Chemical modification is carried out with reactions such as condensation or redox.
The introducing of biomass acidic-group at present mainly uses esterification process, and esterifying reagent is mainly oleum, chlorine sulphur Acid, sulfur trioxide etc., solvent for use are mainly dimethyl sulfoxide, n,N-Dimethylformamide, pyridine etc., air pollution weight, solvent Severe toxicity and difficult recycling, do not meet environmentally protective requirement.
Summary of the invention
The purpose of the present invention is being comprehensively utilized for biological material, uses with biomass powder as basic material, be prepared as Biomass acid material.
The purpose of the present invention can be achieved by the following measures:
A kind of biomass acid material, it is obtained after being reacted by biological material with formylsalicylic acid, wherein the biological material Contain one or more of active group hydroxyl, amino, aldehyde radical or ester group.
Biological material in the present invention includes but is not limited to one of coconut shell flour, wood powder, bamboo powder or straw powder or several Kind.
Formylsalicylic acid in the present invention includes but is not limited to one of glyoxalic acid, malonaldehydic acid, succinic semialdehydic acid or uronic acid or several Kind.
In a preferred embodiment, the reaction temperature in the present invention is 0~80 DEG C, is further 30~80 DEG C.
In a preferred solution, 0.1~100h in the present invention, further reaction time are 0.5~20h.
Above-mentioned reaction carries out in alcohols solvent methanol, ethyl alcohol or propyl alcohol, biological material, formylsalicylic acid and alcohols solvent Mass ratio is 1: 0.1~2: 1~100, preferably 1: 0.1~2: 1~30.Alcohols solvent preferably uses ethyl alcohol.
The present invention further discloses a kind of preparation methods of above-mentioned biomass acid material: biological material and formylsalicylic acid exist It is made in alcohols solvent in 0~80 DEG C of 0.1~100h of reaction.
In preparation method, the selection of each raw material and the selection of reaction condition are as described above.
The surface acidity of the biomass acid material, the surface acidity of biomass acid material of the present invention are measured in terms of surface acidity Value is 1~6.
Biomass acid material of the present invention, what is utilized is the leftover pieces of natural plant resource, does not need additionally to increase Resource consumption meets recycling economy requirement.Cheap, the matter of the made existing biological material of biomass acid material use of the present invention Light and porous characteristic can be used as catalyst and be used in the various organic reactions such as esterification, this abundant and cheap material Also in terms of the production for bio-fuel, biological-based chemicals, biomaterial, food etc. can be converted.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment 1:
In flask, it is put into coconut shell flour, glyoxalic acid and ethyl alcohol, mass ratio 1:0.5:10, reaction temperature is 60 DEG C, instead It is 2 hours between seasonable, filters to obtain acid coconut husk powder material, yield 92%, surface acidity 3.5.
Embodiment 2:
In flask, it is put into wood powder, malonaldehydic acid and ethyl alcohol, mass ratio 1:2:20, reaction temperature is 78 DEG C, when reaction Between 10 hours, filter to obtain acid wood powder material, yield 98%, surface acidity 3.6.
Embodiment 3:
In flask, it is put into bamboo powder, uronic acid and ethyl alcohol, mass ratio 1:0.2:3, reaction temperature is 30 DEG C, when reaction Between be 2 hours, filter to obtain acid coconut husk powder material, yield 81%, surface acidity 4.1.
Comparative example 1:
In flask, it is put into bamboo powder, acetic acid and ethyl alcohol, mass ratio 1:0.2:3, reaction temperature is 30 DEG C, the reaction time It is 2 hours, filters to obtain coconut husk powder material, yield 91%, surface acidity 6.7.
Embodiment 4
The acid coconut husk powder material that embodiment 1 is obtained is heated, stirs and is returned to having as the catalyst of esterification It flows and 10mol acetic acid and 30mol n-butanol and 25g catalyst is added in the reaction flask of device, under stiring at 117-118 DEG C Reflux water-dividing reaction, reacts 2.5h, esterification yield 85%.
Using the material that comparative example 1 obtains as the catalyst of esterification, under equal conditions esterification yield is lower than 30%.
Only to explain more typical example of the invention as described in embodiment, not the present invention is made in any form Limitation, it is all to make any modification or change for the present invention under identical spirit, it is intended to be included in that the invention is intended to protect Within the scope of shield, i.e., with those skilled in the art, it can not depart from and its parameter is made into different journeys under basic principle of the invention The variation of degree, to scheme to reach equivalent or similar effect, so it should all be considered as being defined without departing from above-described the scope of the patents In.

Claims (10)

1. a kind of biomass acid material, it is characterised in that it is obtained after being reacted by biological material with formylsalicylic acid, wherein the life Material contains one or more of active group hydroxyl, amino, aldehyde radical or ester group;The biological material is selected from coconut husk One or more of powder, wood powder, bamboo powder or straw powder.
2. biomass acid material according to claim 1, it is characterised in that the formylsalicylic acid be selected from glyoxalic acid, malonaldehydic acid, One or more of succinic semialdehydic acid or uronic acid.
3. biomass acid material according to claim 1, it is characterised in that its reaction temperature is 0~80 DEG C, the reaction time For 0.1~100h.
4. biomass acid material according to claim 3, it is characterised in that its reaction temperature is 30~80 DEG C, the reaction time For 0.5~20h.
5. biomass acid material according to claim 1, it is characterised in that reaction is in alcohols solvent methanol, ethyl alcohol or propyl alcohol Middle progress, the mass ratio of biological material, formylsalicylic acid and alcohols solvent are 1: 0.1~2: 1~100.
6. biomass acid material according to claim 5, it is characterised in that biological material, formylsalicylic acid and alcohols solvent Mass ratio is 1: 0.1~2: 1~30.
7. biomass acid material according to claim 1, it is characterised in that the surface acid angle value of the material is 1~6.
8. a kind of preparation method of biomass acid material described in claim 1, it is characterised in that biological material and formylsalicylic acid It is being made in alcohols solvent in 0~80 DEG C of 0.1~100h of reaction;The biological material be selected from coconut shell flour, wood powder, bamboo powder, Or one or more of straw powder.
9. the preparation method of biomass acid material according to claim 8, it is characterised in that the formylsalicylic acid is selected from acetaldehyde One or more of acid, malonaldehydic acid, succinic semialdehydic acid or uronic acid;The alcohols solvent is methanol, ethyl alcohol or propyl alcohol;Biological material The mass ratio of material, formylsalicylic acid and alcohols solvent is 1: 0.1~2: 1~100.
10. the preparation method of biomass acid material according to claim 8, it is characterised in that its reaction temperature is 30~80 DEG C, the reaction time is 0.5~20h.
CN201710480372.2A 2017-06-22 2017-06-22 A kind of biomass acid material and preparation method thereof Active CN107417930B (en)

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CN107417930B true CN107417930B (en) 2019-11-05

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Publication number Priority date Publication date Assignee Title
UA116630C2 (en) * 2012-07-03 2018-04-25 Ксілеко, Інк. METHOD OF CONVERTING SUGAR TO FURFURYL ALCOHOL
EP2992041B1 (en) * 2013-05-03 2020-01-08 Virdia, Inc. Methods for treating lignocellulosic materials
CN106245397B (en) * 2016-07-28 2017-12-05 盐城市北鸥生化能源科技有限公司 A kind of method of Cotton Stalk high value synthesis refining

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Address after: 211599 No.52, Shidai Avenue, Liuhe Economic Development Zone, Nanjing, Jiangsu Province

Patentee after: Nanjing Han flag new material Limited by Share Ltd

Address before: 211505 Jiangsu Province, Nanjing city Liuhe District Longchi street Xiongzhou Road No. 399 Building 2 unit 402 glorious Park Room 301

Patentee before: Nanjing Han Qi novel material Science and Technology Ltd.

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Denomination of invention: The invention relates to a biomass acid material and a preparation method thereof

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