CN106336386A - Method for synthesizing furan diacid from biomass raw material - Google Patents
Method for synthesizing furan diacid from biomass raw material Download PDFInfo
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- CN106336386A CN106336386A CN201610578505.5A CN201610578505A CN106336386A CN 106336386 A CN106336386 A CN 106336386A CN 201610578505 A CN201610578505 A CN 201610578505A CN 106336386 A CN106336386 A CN 106336386A
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- furans diacid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- Organic Chemistry (AREA)
- Furan Compounds (AREA)
Abstract
The invention discloses a method for synthesizing furan diacid from a biomass raw material. The method comprises the following steps: synthesizing 5-hydroxymethyl furfural from lignocellulose by adopting a solid acid catalyst; and oxidizing 5-hydroxymethyl furfural by adopting a supported catalyst to form furan diacid, filtering out the obtained product, and separating the catalysts and the liquid product. The new method for producing furan diacid through a biomass route is developed in the invention.
Description
Technical field
The invention belongs to the field of living beings chemicals is and in particular to a kind of non-food organism matter raw material produces furans two
The method of acid.
Background technology
Poly terephthalic acid dimethyl ester (pet) is a kind of important macromolecule raw material, extensively applies in the world.Existing skill
In art, with paraxylene as raw material, paraxylene produces mainly with oil as raw material synthesis pet.China is a net import of oil
State, external energy dependency degree is up to more than 60%, situation very severe.With these non-renewable fossil energies gradually
Exhaustion, makes full use of renewable, degradable resource, and becoming the important raw material of industry by the method for chemical synthesis becomes
Solve the effective means of resource exhaustion and environmental pollution.The biomass materials such as stalk are in nature rich reserves, cheap,
It is important biomass resource, the chemicals of high added value can be synthesized by chemical method, become biomass resource and close
The important channel that reason utilizes.China is a large agricultural country, produces stalk per year about at 700,000,000 tons about, is a kind of economical and easily available
Agriculture waste raw material.Therefore, producing furans diacid with biomass material is to meet economy and social sustainable development, reduces ring
The only way of border pollution.
Furfuran compound is a kind of Important Platform small molecule based on living beings.As 5 hydroxymethyl furfural can directly be turned
Turn to the various levulic acids (la) with economic worth, 2,5 one dimethyl furans (dmf), FDCA (fdca)
Etc. high added value compound it is considered to be a kind of dive between the most exploitation between living beings chemistry and petroleum industry organic chemistry
The living beings platform chemicals of power.With platform chemicals 5 hydroxymethyl furfural as raw material, through one-step synthesis method furans diacid it is
The method being worth attempting.
Some have been had to aoxidize the report of furans diacid processed with regard to 5 hydroxymethyl furfural both at home and abroad, but with lignocellulose raw material
Synthesis furans diacid is rarely reported.The present invention is with lignocellulosic as raw material, through hydrolyzing and aoxidizing two reactions steps, permissible
Obtain the furans diacid of higher yields, thus providing a new way of green synthesizing furans diacid from unedible living beings
Footpath.
Content of the invention
The technical problem solving: proposed by the present invention is the new side that a kind of unedible biomass material produces furans diacid
Method, its objective is to solve the problems, such as biomass material higher value application, is characterized in that the present invention combines catalyzing hydrolysis, catalysis oxidation
Etc. method coupling, there is the features such as reaction condition is gentle, reaction process is green.
Technical scheme: a kind of biomass material synthesizes the method for furans diacid it is characterised in that comprising the following steps:
(1) adopt solid acid catalyst, in a two-phase system, 5 hydroxymethyl furfural prepared by catalysis biomass raw material, institute
The product obtaining filters, and reclaims catalyst and product liquid；
(2) by step 1 gained product liquid through filtering, adsorbing contaminant, add the bimetallic catalyst containing pd, through peroxide
Change reaction, furans diacid can be synthesized.
2. the method that biomass material according to claim 1 synthesizes furans diacid, is characterized in that described solid
Acid catalyst, is fepo4、sc2(po4)3One kind.
3rd, the method that biomass material according to claim 1 synthesizes furans diacid, is characterized in that described two-phase
System, wherein one is mutually water, and another is mutually oxolane, n-butanol, toluene, the one or two kinds of component of 2- butanol.
4th, the method that biomass material according to claim 1 synthesizes furans diacid, is characterized in that described load
Type metallic catalyst, its carrier be hydrotalcite, silica, aluminum oxide, titanium oxide, zirconium oxide, magnesia, montmorillonite, activated carbon,
One of CNT, Graphene.
5th, the method that biomass material according to claim 1 synthesizes furans diacid, is characterized in that double containing pd
Metallic catalyst, its group is divided into the one or two kinds of component of rh, ru, ir, pt, au, cu, ag, fe, co, ni, re, mo.
6th, the method that biomass material according to claim 1 synthesizes furans diacid, is characterized in that described biology
Matter raw material, is wheat stalk, maize straw, wood chip, broomcorn straw, oil tea shell, one kind of rice straw.
Beneficial effect: the present invention, with reproducible living beings as raw material, produces furans two through hydrolysis, two steps of oxidation
Acid.The present invention has developed a kind of new way with living beings for Material synthesis furans diacid.
Specific embodiment
Embodiment 1
By 200mg microcrystalline cellulose, 20mg fepo4For catalyst, add 10ml deionized water and 30mlthf, add
3.5gnacl, 160 DEG C are reacted 2 hours, have reacted filtration, can get the aqueous solution that yield is higher than 40% 5 hydroxymethyl furfural.
Water in product liquid is evaporated, obtains pressed powder.Pressed powder is dissolved in the aqueous solution, add pd-au/ht (1wt%pd,
3.7wt.%au), 126mg naoh, 50ml deionized water, in rotating speed 550r/min, is passed through the o of 60ml/min2, anti-at 60 DEG C
Answer 360min, can get the furans diacid that yield is more than 90%.
Embodiment 2
By 1g microcrystalline cellulose, 50mg fepo4For catalyst, add 10ml deionized water and 30mlthf, add 3.5g
Nacl, 160 DEG C are reacted 2 hours, have reacted filtration, can get the aqueous solution that yield is higher than 50% 5 hydroxymethyl furfural.By liquid
Water in body product is evaporated, and obtains pressed powder.Pressed powder is dissolved in the aqueous solution, add pd-au/ht (1wt%pd,
3.7wt.%au), 126mgnaoh, 50ml deionized water, in rotating speed 550r/min, is passed through the o of 60ml/min2, react at 60 DEG C
360min, can get the furans diacid that yield is more than 90%.
Embodiment 3
By 1g wheat stalk, 20mg fepo4With 20mg nah2po4For catalyst, add 10ml deionized water and
30mlthf, 3.5g nacl, 170 DEG C are reacted 2 hours, have reacted filtration, can get the 5 hydroxymethyl furfural that yield is higher than 42%
The aqueous solution.Water in product liquid is evaporated, obtains pressed powder.Pressed powder is dissolved in the aqueous solution, adds pd-au/ht
(1wt%pd, 5.0wt.%au), 126mgnaoh, 50ml deionized water, in rotating speed 550r/min, it is passed through the o of 60ml/min2,
React 360min at 60 DEG C, can get the furans diacid that yield is more than 90%.
Embodiment 4
By 1g oil tea husk as raw material, 50mgfepo4And 20mgnah2po4For catalyst, add 10ml deionized water and
30mlthf, adds 3.5g nacl, and 170 DEG C are reacted 2 hours, have reacted filtration, can get the 5- methylol that yield is higher than 45%
The aqueous solution of furfural.Water in product liquid is evaporated, obtains pressed powder.Pressed powder is dissolved in the aqueous solution, adds pd-
Au/ht (1wt%pd, 5.0wt.%au), 126mgnaoh, 50ml deionized water, in rotating speed 550r/min, it is passed through 60ml/min
O2, react 360min at 60 DEG C, can get the furans diacid that yield is more than 90%.
Embodiment 5
By 1g maize straw, 50mgfepo4With 20mg nah2po4For catalyst, add 10ml deionized water and
30mlthf, adds 3.5g nacl, and 170 DEG C are reacted 2 hours, have reacted filtration, can get the 5- methylol that yield is higher than 45%
The aqueous solution of furfural.Water in product liquid is evaporated, obtains pressed powder.Pressed powder is dissolved in the aqueous solution, adds pd-
Au/ht (1wt%pd, 5.0wt.%au), 126mgnaoh, 50ml deionized water, in rotating speed 550r/min, it is passed through 60ml/min
O2, react 360min at 60 DEG C, can get the furans diacid that yield is more than 90%.
The above is only the preferred embodiment of the present invention it is noted that ordinary skill people for the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (6)
1. a kind of biomass material synthesizes the method for furans diacid it is characterised in that comprising the following steps:
(1) adopt solid acid catalyst, in a two-phase system, 5 hydroxymethyl furfural prepared by catalysis biomass raw material, gained
Product filters, and reclaims catalyst and product liquid；
(2) by step 1 gained product liquid through filtering, adsorbing contaminant, add the bimetallic catalyst containing pd, through peroxidation
Should, furans diacid can be synthesized.
2. the method that biomass material according to claim 1 synthesizes furans diacid, is characterized in that described solid acid is urged
Agent, is fepo4、sc2(po4)3One kind.
3. the method that biomass material according to claim 1 synthesizes furans diacid, is characterized in that described two-phase system,
Wherein one is mutually water, and another is mutually oxolane, n-butanol, toluene, the one or two kinds of component of 2- butanol.
4. the method that biomass material according to claim 1 synthesizes furans diacid, is characterized in that described load type gold
Metal catalyst, its carrier is hydrotalcite, silica, aluminum oxide, titanium oxide, zirconium oxide, magnesia, montmorillonite, activated carbon, carbon are received
One of mitron, Graphene.
5. the method that biomass material according to claim 1 synthesizes furans diacid, is characterized in that the bimetallic containing pd
Catalyst, its group is divided into the one or two kinds of component of rh, ru, ir, pt, au, cu, ag, fe, co, ni, re, mo.
6. the method that biomass material according to claim 1 synthesizes furans diacid, is characterized in that described living beings are former
Material, is wheat stalk, maize straw, wood chip, broomcorn straw, oil tea shell, one kind of rice straw.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610578505.5A CN106336386A (en) | 2016-07-20 | 2016-07-20 | Method for synthesizing furan diacid from biomass raw material |
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| CN201610578505.5A CN106336386A (en) | 2016-07-20 | 2016-07-20 | Method for synthesizing furan diacid from biomass raw material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109894140A (en) * | 2017-12-07 | 2019-06-18 | 浙江糖能科技有限公司 | A kind of preparation method and its catalytic applications of solid base hydrotalcite supported precious metal catalyst |
| CN113275019A (en) * | 2021-06-04 | 2021-08-20 | 云南大学 | Magnetic nickel-cobalt oxide supported gold catalyst, preparation method and application thereof, and preparation method of 2, 5-furandicarboxylic acid |
| CN114605359A (en) * | 2022-03-09 | 2022-06-10 | 苏州禾广吉智能装备有限公司 | Method for preparing FDCA (fully drawn yarn) and total bio-based filler by using non-grain biomass raw material |
| CN115710242A (en) * | 2022-11-30 | 2023-02-24 | 盱眙凹土能源环保材料研发中心 | Method for preparing 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural |
| CN117801849A (en) * | 2023-12-15 | 2024-04-02 | 南京林业大学 | Method for producing biofuel and co-producing activated carbon microspheres by using camellia oleifera shell raw material |
-
2016
- 2016-07-20 CN CN201610578505.5A patent/CN106336386A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109894140A (en) * | 2017-12-07 | 2019-06-18 | 浙江糖能科技有限公司 | A kind of preparation method and its catalytic applications of solid base hydrotalcite supported precious metal catalyst |
| CN113275019A (en) * | 2021-06-04 | 2021-08-20 | 云南大学 | Magnetic nickel-cobalt oxide supported gold catalyst, preparation method and application thereof, and preparation method of 2, 5-furandicarboxylic acid |
| CN114605359A (en) * | 2022-03-09 | 2022-06-10 | 苏州禾广吉智能装备有限公司 | Method for preparing FDCA (fully drawn yarn) and total bio-based filler by using non-grain biomass raw material |
| CN114605359B (en) * | 2022-03-09 | 2024-05-31 | 苏州禾广吉智能装备有限公司 | Method for preparing FDCA and full bio-based filler by using non-grain biomass raw material |
| CN115710242A (en) * | 2022-11-30 | 2023-02-24 | 盱眙凹土能源环保材料研发中心 | Method for preparing 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural |
| CN117801849A (en) * | 2023-12-15 | 2024-04-02 | 南京林业大学 | Method for producing biofuel and co-producing activated carbon microspheres by using camellia oleifera shell raw material |
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| WD01 | Invention patent application deemed withdrawn after publication |
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