CN105646404B - CO2The method for cooperateing with metal ion catalysis conversion carbohydrate or biomass - Google Patents
CO2The method for cooperateing with metal ion catalysis conversion carbohydrate or biomass Download PDFInfo
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- CN105646404B CN105646404B CN201610169544.XA CN201610169544A CN105646404B CN 105646404 B CN105646404 B CN 105646404B CN 201610169544 A CN201610169544 A CN 201610169544A CN 105646404 B CN105646404 B CN 105646404B
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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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
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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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
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Abstract
The invention belongs to field of energy and chemical technologys, disclose a kind of CO2The method for cooperateing with metal ion catalysis conversion carbohydrate or biomass.The method is：Carbohydrate or biomass material and water are added in reactor, metal chloride is then added, reactor is sealed, is passed through the CO of 2~10MPa at room temperature2, then heat to 140~200 DEG C and react 5~180 minutes, obtain organic acid and Furnan products；The metal chloride refers to the villaumite or aluminium chloride of transition metal.The present invention is with CO2It is catalyst with metal salt, Synergistic degradation simultaneously converts carbohydrate or biomass material, and obtains industrial chemicals lactic acid, formic acid, levulic acid, furfural and the 5 hydroxymethyl furfural of high added value, realizes CO2With carbohydrate or the recycling of biomass material, have many advantages, such as it is simple for process, it is environmentally protective.
Description
Technical field
The invention belongs to field of energy and chemical technologys, and in particular to a kind of CO2Metal ion catalysis is cooperateed with to convert carbon aquation
The method for closing object or biomass.
Background technology
Using the energy and environmental problem for bringing getting worse, seeking one kind can meet increasingly for the transition of fossil resources
Increase the common objective that the new energy kept ecological balance while energy requirements has become various countries' researcher.Carbon hydrate
Species biomass resource has many advantages, such as to derive from a wealth of sources, is environmental-friendly, cheap, is the desirable feedstock for substituting fossil resources.
Renewable most abundant as reserves in nature of carbohydrate biomass contains carbon resource, and will become liquid fuel and have
The important sources of chemical machine product.Cellulose, hemicellulose and lignin are three big main components of biomass, be in nature most
Abundant non-grain carbohydrate, is catalytically conveted to the chemicals with high added value, as 5 hydroxymethyl furfural, lactic acid,
Formic acid, levulic acid etc. are the key that realize human social.
Since Hydrogenbond effect is strong between cellulose, cellulose macromolecule has certain crystalline texture so that carbon hydrate
The conversion of species biomass becomes difficult.Addition strong acid or highly basic can effectively facilitate the hydrolysis of carbohydrate biomass, enhancing
Reaction efficiency reduces reaction temperature and reduces the reaction time.But strong acid and strong base can cause equipment to corrode, to equipment and materials requirement
Height increases equipment cost and cost of sewage disposal.CO2It derives from a wealth of sources, is cheap and easy to get, is nontoxic and nonflammable, being a kind of green
Color compound.Supercritical carbon dioxide or high pressure CO2Biomass material is handled, using CO2It is dissolved in the weak acid and high pressure of water generation
The physical action of gas increases the yield of subsequent fermentation hydrocellulose glucose.
By CO2The carbonic acid hydrolysis generated in situ is combined with the catalytic phase of metal ion, and cellulose of connecting hydrolyzes, is single
Sugar conversion and 5 hydroxymethyl furfural hydration reaction, can quickly produce 5 hydroxymethyl furfural and formic acid, lactic acid, second in a mild condition
The small molecular organic acids such as acyl propionic acid and acetic acid.Strong acid, which is substituted, with carbonic acid realizes that carbohydrate biomass efficient catalytic is converted into
Micromolecular compound have very significant superiority, the corrosion to equipment can be greatly reduced, not only reduce sewage disposal at
This, reduces cost of material, and this technique will have huge potentiality.
Invention content
In order to solve the disadvantage that the prior art and shortcoming, the purpose of the present invention is to provide a kind of CO2Cooperate with metal
The method that ionic catalysis converts carbohydrate or biomass.
The object of the invention is achieved through the following technical solutions：
A kind of CO2The method for cooperateing with metal ion catalysis conversion carbohydrate or biomass, including following preparation process：
Carbohydrate or biomass material and water are added in reactor, metal chloride is then added, reactor is sealed, in room temperature
Under be passed through the CO of 2~10MPa2, then heat to 140~200 DEG C and react 5~180 minutes, obtain organic acid and furfural class
Close object；The metal chloride refers to the villaumite or aluminium chloride of transition metal.
Preferably, the carbohydrate includes polysaccharide such as starch, cellulose, hemicellulose, monosaccharide such as glucose, wood
Sugar, fructose, oligosaccharides such as cellobiose, cellotriose, cellotetrose or xylobiose etc.；The biomass material include stalk,
Cereal leather shell, bagasse, potato, sawdust, paper pulp or city fiber rubbish etc..
Preferably, it is 20~200 mesh that the biomass material is first crushed to fineness before reactor is added.
The CO2For pure CO2, or directly using from coal chemical industry, coal-burning power plant, coke-oven plant, steel mill Deng great energy consumptions factory
The CO discharged2Exhaust gas.Other compositions such as SOx, NOx in exhaust gas etc. do not influence hydro-thermal reaction, and can be with ionic state shape
Formula captures in water, eliminates the desulfurization removing nitric technique in traditional waste treatment, and the acid of generation is also conducive to the degradation turn of cellulose
Change.
The organic acid is detached according to different boiling through vacuum distillation, obtains lactic acid, formic acid and levulic acid；Described
Furnan products are separated by extraction, and obtain furfural and 5 hydroxymethyl furfural (HMF).
Preferably, the addition of the water is the 20%~60% of reactor total capacity, the carbohydrate or biology
The addition of matter raw material is the 10%~40% of water quality, the carbohydrate or biomass material and metal in metal chloride
Mass of ion ratio is 100:(0.5~10).
The principle of the present invention is：Under hydrothermal condition, carbohydrate or biomass material are in CO2Generated in-situ carbonic acid and
It degrades under the catalysis of metal salt and is converted into the organic acids such as lactic acid, formic acid and levulic acid and furfural, 5 hydroxymethyl furfural
Deng.Vacuum distillation separation is carried out according to the different boiling of lactic acid, formic acid and levulic acid, obtains lactic acid, formic acid and levulic acid,
It is separated by extraction to obtain furfural and 5 hydroxymethyl furfural.
The present invention preparation method and obtained product has the following advantages that and advantageous effect：
(1) present invention is under hydrothermal conditions, with CO2It is catalyst with metal chloride, Synergistic degradation simultaneously converts carbon aquation
Object or biomass material are closed, and obtains industrial chemicals lactic acid, formic acid, levulic acid, furfural and the 5- methylol chaffs of high added value
Aldehyde, therefore the method for the present invention can realize CO2With the recycling of carbohydrate or biomass material, and with simple for process,
It is easy to operate, the advantages that non-secondary pollution；
(2) since the biomass material of the present invention is discarded from biomass such as stalk, husk, sawdust, waste paper and bagasse
Object, can realize the treatment of wastes with processes of wastes against one another, and generating process only needs to add a small amount of metal salt can meet technique, of low cost, can generate
Good economic benefit；
(3) it is discharged using from coal chemical industry, coal-burning power plant, coke-oven plant, steel mill Deng great energy consumptions factory by the present invention
CO2, therefore derive from a wealth of sources and be easy to get；In the hydrothermal reaction process of the present invention, the harmful constituent contained in these exhaust gas is such as
SOx, NOx etc. capture in water in the form of ionic state, and these components exist and do not influenced on hydro-thermal reaction, eliminate biography
Desulfurization removing nitric technique in exhaust-gas treatment of uniting realizes the further utilization to exhaust gas, and there is fabulous social benefit and economy to imitate
Benefit.
Description of the drawings
Fig. 1 is CO under the differential responses time in embodiment 12And CrCl3The hydro-thermal reaction efficiency of pcr product of the lower glucose of catalysis
(left side) and independent CrCl3Lower yield (right side) comparison diagram of catalysis；
Fig. 2 is CO under the differential responses time in embodiment 12And CrCl3The hydro-thermal reaction efficiency of pcr product (left side) of the lower fructose of catalysis
With independent CrCl3Lower yield (right side) comparison diagram of catalysis；
Fig. 3 be in embodiment 2 when the reaction time is 40min CO2And AlCl3The hydro-thermal reaction product breast of the lower xylose of catalysis
The yield of acid and formic acid and independent CrCl3The lower yield comparison diagram of catalysis；
Fig. 4 is CO under the differential responses time in embodiment 32And CrCl3The hydro-thermal reaction efficiency of pcr product of the lower cellulose of catalysis
(left side) and independent CrCl3Lower yield (right side) comparison diagram of catalysis；
Fig. 5 be in embodiment 4 when the reaction time is 180min CO2And CuCl2The hydro-thermal reaction product of the lower cellulose of catalysis
Yield and independent CuCl2The lower yield comparison diagram of catalysis；
Fig. 6 be in embodiment 5 when the reaction time is 180min CO2And ZnCl2The hydro-thermal reaction product of the lower cellulose of catalysis
Yield and independent ZnCl2The lower yield comparison diagram of catalysis.
Specific implementation mode
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
Using glucose as raw material.Water is first loaded in the reactor, the amount of water is that filling rate is multiplied by obtained by reactor volume,
Filling rate is controlled 33%.Then the glucose of water quality 10% is added, with Cr3+Quality meter be added glucose quality 0.9%
CrCl3, reactor is sealed, CO is passed through2, hydrothermal reaction condition is：160 DEG C of temperature is reacted 0~180 minute under pressure 4MPa.
Under the differential responses time shown in efficiency of pcr product such as Fig. 1 (left side).With CrCl under the same terms3It is catalyzed the hydro-thermal reaction of glucose (not
It is passed through CO2) as a contrast, under the differential responses time shown in efficiency of pcr product such as Fig. 1 (right side).As seen from Figure 1, the reaction time is
When 50min, CO2And CrCl3The hydro-thermal reaction efficiency of pcr product of glucose is under catalysis：7.9% lactic acid, 43.7% formic acid,
22.9% levulic acid, 6.4%HMF；And independent CrCl3The reaction time for reaching identical efficiency of pcr product under catalysis is
120min.It can be seen that CO2Addition greatly improve the transformation efficiency of glucose.
Using fructose as raw material under similarity condition, CO under the differential responses time is tested2And CrCl3Catalysis reaction yield, as a result
As shown in Fig. 2 (left side)；With independent CrCl under the same terms3Be catalyzed fructose hydro-thermal reaction as a contrast, under the differential responses time
Shown in efficiency of pcr product such as Fig. 2 (right side).As seen from Figure 2, when the reaction time is 30min, CO2And CrCl3The water of the lower fructose of catalysis
Thermal response efficiency of pcr product is：8.8% lactic acid, 42.2% formic acid, 22.1% levulic acid, 11.6%HMF；And independent CrCl3It urges
The reaction time for reaching identical efficiency of pcr product under change is 120min.It can be seen that CO2Addition greatly improve fructose
Transformation efficiency.
Embodiment 2
Using xylose as raw material.Water is first loaded in the reactor, and the amount of water is that filling rate is multiplied by obtained by reactor volume, is filled out
Rate control is filled 33%.Then the xylose of water quality 10% is added, with Al3+Quality meter xylose quality 0.5% is added
AlCl3, reactor is sealed, CO is passed through2, hydrothermal reaction condition is：160 DEG C of temperature is reacted 40 minutes under pressure 4MPa.And with phase
With independent AlCl under the conditions of3As a contrast, the yield comparison diagram of product lactic acid and formic acid is such as the hydro-thermal reaction of catalysis xylose
Shown in Fig. 3.As seen from Figure 3, CO2Addition greatly improve the transformation efficiency of xylose.
Embodiment 3
Using cellulose as raw material.Water is first loaded in the reactor, the amount of water is that filling rate is multiplied by obtained by reactor volume,
Filling rate is controlled 33%.Then the cellulose of water quality 10% is added, with Cr3+Quality meter cellulose quality 0.9% is added
CrCl3, reactor is sealed, CO is passed through2, hydrothermal reaction condition is：160 DEG C of temperature is reacted 0~180 minute under pressure 4MPa.
Under the differential responses time shown in efficiency of pcr product such as Fig. 4 (left side).With CrCl under the same terms3The hydro-thermal reaction of catalytic cellulose is (not
It is passed through CO2) as a contrast, under the differential responses time shown in efficiency of pcr product such as Fig. 4 (right side).As seen from Figure 4, the reaction time is
When 70min, CO2And CrCl3The hydro-thermal reaction efficiency of pcr product of cellulose is under catalysis：10.4% lactic acid, 43.3% formic acid,
31.7% levulic acid；And independent CrCl3The reaction time for reaching identical efficiency of pcr product under catalysis will be more than 180min.By
This is as it can be seen that CO2Addition greatly improve the transformation efficiency of cellulose.
Embodiment 4
Using cellulose as raw material.Water is first loaded in the reactor, the amount of water is that filling rate is multiplied by obtained by reactor volume,
Filling rate is controlled 20%.Then the cellulose of water quality 10% is added, with Cu2+Quality meter cellulose quality 1% is added
CuCl2, reactor is sealed, CO is passed through2, hydrothermal reaction condition is：180 DEG C of temperature is reacted 180 minutes under pressure 4MPa, is reacted
Efficiency of pcr product is：36.6% glucose, 4.4% lactic acid, 13.5% formic acid, 9.8% levulic acid.And under the same terms with list
Only CuCl2As a contrast, efficiency of pcr product comparison diagram is as shown in Figure 5 for the hydro-thermal reaction of catalytic cellulose.As seen from Figure 5,
CO2Addition greatly improve the transformation efficiency of cellulose.
Embodiment 5
Using cellulose as raw material.Water is first loaded in the reactor, the amount of water is that filling rate is multiplied by obtained by reactor volume,
Filling rate is controlled 33%.Then the cellulose of water quality 10% is added, with Zn2+Quality meter cellulose quality 1% is added
ZnCl2, reactor is sealed, CO is passed through2, hydrothermal reaction condition is：200 DEG C of temperature is reacted 180 minutes under pressure 4MPa, is reacted
Efficiency of pcr product is：8.3% glucose, 4.8% lactic acid, 15.3% formic acid, 2.3% acetic acid, 7.1% levulic acid, 5.9%HMF.
And under the same terms with independent ZnCl2The hydro-thermal reaction of catalytic cellulose as a contrast, efficiency of pcr product comparison diagram such as Fig. 6 institutes
Show.As seen from Figure 6, CO2Addition greatly improve the transformation efficiency of cellulose.
Embodiment 6
Using maize straw as raw material.Water is first loaded in the reactor, and the amount of water is multiplied by reactor volume institute for filling rate
, filling rate is controlled 33%.Then the corn stalk pellets (it is 20~200 mesh to be crushed to fineness) of water quality 7% are added, with
Cr3+Quality meter the CrCl of corn stalk pellets quality 1.5% is added3, reactor is sealed, CO is passed through2, hydrothermal reaction condition
For：180 DEG C of temperature is reacted 90 minutes under pressure 4MPa, and reaction product yield is：13.6% lactic acid, 5.2% formic acid, 5.0% second
Acid, 4.1% levulic acid.
Embodiment 7
Using bagasse as raw material.Water is first loaded in the reactor, and the amount of water is that filling rate is multiplied by obtained by reactor volume, is filled out
Rate control is filled 33%.Then the bagasse particle (it is 20~200 mesh to be crushed to fineness) of water quality 10% is added, with Cr3+Matter
The CrCl of bagasse quality 0.9% is added in gauge3, reactor is sealed, CO is passed through2, hydrothermal reaction condition is：180 DEG C of temperature, pressure
It is reacted 90 minutes under 4MPa, reaction product yield is：13.1% lactic acid, 8.3% formic acid, 4.7% acetic acid, 8.0% levulic acid.
Embodiment 8
Using secondary stock as raw material.Water is first loaded in the reactor, the amount of water is that filling rate is multiplied by obtained by reactor volume,
Filling rate is controlled 33%.Then the secondary stock of water quality 10% is added, with Cr3+Quality meter secondary stock quality 0.9% is added
CrCl3, reactor is sealed, CO is passed through2, hydrothermal reaction condition is：160 DEG C of temperature is reacted 90 minutes under pressure 4MPa, is reacted
Efficiency of pcr product is：9.1% lactic acid, 5.63% formic acid, 1.8% acetic acid, 6.0% levulic acid.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (4)
1. a kind of CO2The method for cooperateing with metal ion catalysis conversion of biomass, it is characterised in that including following preparation process：It will give birth to
Raw material of substance and water are added in reactor, and metal chloride is then added, and are sealed reactor, are passed through 2~10MPa's at room temperature
CO2, then heat to 140~200 DEG C and react 5~180 minutes, obtain organic acid and Furnan products；The metal chlorine
Salt refers to the villaumite or aluminium chloride of transition metal；The organic acid according to different boiling through vacuum distillation detach, obtain lactic acid,
Formic acid and levulic acid；The Furnan products are separated by extraction, and obtain furfural or 5 hydroxymethyl furfural；The life
Raw material of substance is stalk, cereal leather shell, bagasse, potato, sawdust, paper pulp or city fiber rubbish.
2. a kind of CO according to claim 12The method for cooperateing with metal chloride catalyzed conversion biomass, it is characterised in that：Institute
It is 20~200 mesh that the biomass material stated first is crushed to fineness before reactor is added.
3. a kind of CO according to claim 12The method for cooperateing with metal ion catalysis conversion of biomass, it is characterised in that：Institute
The CO stated2For pure CO2, or directly utilize the CO from plant emissions2Exhaust gas.
4. a kind of CO according to claim 12The method for cooperateing with metal ion catalysis conversion of biomass, it is characterised in that：Institute
The addition for stating water is the 20%~60% of reactor total capacity, the addition of the biomass material be water quality 10%~
40%, the mass ratio of metal ion is 100 in the biomass material and metal chloride:(0.5~10).
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| CN106045948B (en) * | 2016-06-27 | 2018-08-21 | 田东县浙缘农业科技有限公司 | One kind is by CO2The method that liquid aqueous systems prepare 5 hydroxymethyl furfural |
| CN107118092A (en) * | 2017-05-25 | 2017-09-01 | 华南理工大学 | A kind of method that carbon dioxide collaboration metal oxide oxidation catalyst converts carbohydrate |
| CN110229126B (en) * | 2019-07-25 | 2022-04-26 | 广西科学院 | Based on high temperature high pressure CO2Method for decomposing fructose by system catalysis |
| CN116143731B (en) * | 2022-11-11 | 2024-04-19 | 合肥利夫生物科技有限公司 | Preparation method of 5-hydroxymethylfurfural |
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| CN101774904A (en) * | 2009-12-01 | 2010-07-14 | 同济大学 | Method for preparing formic acid through hydrothermal reduction of CO2 by carbohydrate biomass |
| CN103183653A (en) * | 2011-12-29 | 2013-07-03 | 广西科学院 | Green method for preparation of 5-hydroxymethylfurfural |
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