CN107417930B - A kind of biomass acid material and preparation method thereof - Google Patents
A kind of biomass acid material and preparation method thereof Download PDFInfo
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- 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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- 239000000463 material Substances 0.000 title claims description 34
- 239000002253 acid Substances 0.000 title claims description 33
- 239000002028 Biomass Substances 0.000 title claims description 22
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000000843 powder Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012620 biological material Substances 0.000 claims description 16
- 244000060011 Cocos nucifera Species 0.000 claims description 12
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- OJOMAYXJUJFWGZ-UHFFFAOYSA-N 2-formyloxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1OC=O OJOMAYXJUJFWGZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000001298 alcohols Chemical class 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 7
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 7
- 241001330002 Bambuseae Species 0.000 claims description 7
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 7
- 239000011425 bamboo Substances 0.000 claims description 7
- 239000010903 husk Substances 0.000 claims description 7
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 5
- OAKURXIZZOAYBC-UHFFFAOYSA-N 3-oxopropanoic acid Chemical compound OC(=O)CC=O OAKURXIZZOAYBC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 3
- 235000013312 flour Nutrition 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000010902 straw Substances 0.000 claims description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 241001662103 Cryptocarya corrugata Species 0.000 description 1
- 229920000832 Cutin Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000241602 Gossypianthus Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 244000021150 Orbignya martiana Species 0.000 description 1
- 235000014643 Orbignya martiana Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- HYJODZUSLXOFNC-UHFFFAOYSA-N [S].[Cl] Chemical compound [S].[Cl] HYJODZUSLXOFNC-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002916 wood waste Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710480372.2A CN107417930B (en) | 2017-06-22 | 2017-06-22 | A kind of biomass acid material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710480372.2A CN107417930B (en) | 2017-06-22 | 2017-06-22 | A kind of biomass acid material and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN107417930A CN107417930A (en) | 2017-12-01 |
| CN107417930B true CN107417930B (en) | 2019-11-05 |
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Family Cites Families (3)
| 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 |
| AU2013388054B2 (en) * | 2013-05-03 | 2017-09-21 | 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 Effective date of registration: 20210421 Granted publication date: 20191105 Pledgee: Nanjing Liuhe Branch of Jiangsu Bank Co.,Ltd. Pledgor: NANJING HANQI NEW MATERIALS Co.,Ltd. Registration number: Y2021980002865 |
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Date of cancellation: 20220329 Granted publication date: 20191105 Pledgee: Nanjing Liuhe Branch of Jiangsu Bank Co.,Ltd. Pledgor: NANJING HANQI NEW MATERIALS Co.,Ltd. Registration number: Y2021980002865 |