CN105693483B - The method of aromatic aldehyde adsorbing separation in lignin oxidation's liquid - Google Patents
The method of aromatic aldehyde adsorbing separation in lignin oxidation's liquid Download PDFInfo
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- CN105693483B CN105693483B CN201610021476.2A CN201610021476A CN105693483B CN 105693483 B CN105693483 B CN 105693483B CN 201610021476 A CN201610021476 A CN 201610021476A CN 105693483 B CN105693483 B CN 105693483B
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- lignin
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- aromatic aldehyde
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/79—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- Compounds Of Unknown Constitution (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a kind of method of aromatic aldehyde adsorbing separation in lignin oxidation's liquid, using the lignocellulosic rich in lignin as raw material, after wet method catalytic oxidation, lignin oxidation's liquid is prepared；Lignin oxidation liquid pH is adjusted to slant acidity, then using Aromatic aldehyde compound in attapulgite adsorbing separation lignin oxidation liquid；Finally Aromatic aldehyde compound of the absorption on attapulgite is eluted with eluant, eluent, realizes Aromatic aldehyde compound from the initial gross separation in catalytic lignin oxidative breakdown product.The present invention is adsorbed by attapulgite, and initial gross separation goes out commercially valuable parahydroxyben-zaldehyde, vanillic aldehyde and syringaldehyde from catalytic lignin oxidative breakdown product, simplifies the separation-extraction technology of lignin degradation products.
Description
Technical field
The invention belongs to technical field of biomass chemical engineering, specifically, it is related to aromatic aldehyde absorption point in lignin oxidation's liquid
From method.
Background technology
Lignin in lignocellulosic material can be degraded to low molecule quantization product by solvolysis, such as fragrant
Lan Su, benzene and phenol and their homologue.Low molecule product after the oxidized degraded of lignin has parahydroxyben-zaldehyde, perfume (or spice)
Oxalaldehyde, syringaldehyde, guaiacol, acetovanillon and acetyl group syringone etc., wherein three kinds of key aroma aldehyde account for altogether 90% with
On, but its physicochemical properties is closely similar, and separating difficulty is very big.Using sodium hydrogensulfite and aldehyde compound reaction generation water
The principle of dissolubility sodium hydrogensulfite addition product, the aldehyde compound in reactant is separated with other components, it also requires
To its it is further separate, complex process.Current research is concentrated mainly in the degradation technique of lignin or technique, though
It is related to orient in lignin and is converted into the report of the higher single organic compound of yield, but yield is relatively low and industrialization prospect
It is not clear.Also there is isolating and purifying for the vanillic aldehyde that research focused in Aromatic aldehyde compound, but be also not carried out lignin degradation
Three kinds of primary products --- parahydroxyben-zaldehyde, vanillic aldehyde and syringaldehyde are kept completely separate, and cause certain waste.
Absorption method extensive application in natural product extraction, it has low cost, efficiency high, adsorbent are repeatable to make
With, expend the features such as quantity of solvent is few.Attapulgite, also known as palygorskite（palygorskite）, it is a kind of layer chain transition structure
The clay ore deposit based on magnesium silicate containing Shuifu County, its theoretical chemistry formula is, because of it
Excellent adsorptivity, catalytic, suspension rheological characteristic, fillibility and ion exchangeable etc., are able to extensive use.Using concave convex rod
The initial gross separation from lignin oxidation's liquid of the adsorptivity of soil goes out parahydroxyben-zaldehyde, vanillic aldehyde and syringaldehyde, has not yet to see
Report.
The content of the invention
It is an object of the invention to：There is provided aromatic aldehyde in a kind of lignin oxidation's liquid for the problem of existing for prior art
The method of adsorbing separation, is adsorbed by attapulgite, and initial gross separation goes out to have business from catalytic lignin oxidative breakdown product
Parahydroxyben-zaldehyde, vanillic aldehyde and the syringaldehyde of value, simplify the separation-extraction technology of lignin degradation products.
The present invention technical solution be：Using the lignocellulosic rich in lignin as raw material, through wet method catalysis oxidation
After reaction, lignin oxidation's liquid is prepared；Lignin oxidation liquid pH is adjusted to slant acidity, then using attapulgite adsorbing separation wood
Aromatic aldehyde compound in quality oxidation solution；Under finally Aromatic aldehyde compound of the absorption on attapulgite is eluted with eluant, eluent
Come, realize Aromatic aldehyde compound from the initial gross separation in catalytic lignin oxidative breakdown product.
Wherein, the lignocellulosic material rich in lignin is in corncob, maize straw or wheat straw waste hydrolytic residue
One kind, its key component be lignin.
Wherein, wet method catalytic oxidation condition is：160 ~ 200 DEG C of temperature, 0.5 ~ 1.0MPa of oxygen pressure, reactant
Concentration of lye is 5 ~ 10%, catalyst 0.5 ~ 2%, 60 ~ 180min of reaction time, 100 ~ 300rpm of speed of agitator in system.
Wherein, acid used in the pH of regulation aromatic aldehyde material liquid is one kind in sulfuric acid, hydrochloric acid or phosphoric acid, and mass concentration is
10%。
Wherein, the operating procedure of attapulgite adsorbing separation is：Lignin oxidation's liquid filtering, takes filtrate, regulation filtrate pH
It is worth to 5 ~ 6；Attapulgite calcination in 500 ~ 700 DEG C of Muffle furnaces is cooled to room temperature after 4 hours, then by liquid-solid ratio 50 ~ 100:1 will
Attapulgite is added in lignin oxidation's liquid, is filtered, is taken after being placed in shaking table, 200r/min, 30 DEG C of 1 ~ 10min of concussion absorption
Filter cake；Filter cake mixes with the ethanol solution of mass concentration 95% and is placed in shaking table, 200r/min, mistake after 30 DEG C of 10 ~ 60min of concussion desorption
Filter, filtrate is fragrant aldehyde mixture.
The advantage of the invention is that：
1st, raw materials used lignocellulosic hydrolytic residue is the discarded object of cellulose industry, is synthesized by and initial gross separation
Go out Aromatic aldehyde compound, realize the efficient utilization of lignocellulosic material.
2nd, only need to be to lignin oxidation using the Aromatic aldehyde compound in attapulgite adsorbing separation lignin degradation products
Liquid, which carries out neutralisation treatment, just can directly carry out adsorbing separation, not introduce a large amount of organic solvents, and operating condition is gentle, technique letter
It is single.
3rd, attapulgite clay adsorbent aboundresources used, has absorption in the adsorption separation process of lignin-base aromatic aldehyde
Capacity is big, the gentle good, desorption condition of selectivity, easy regeneration treatment the advantages of.
Brief description of the drawings
Fig. 1 is the adsorbance of aromatic aldehyde in different initial concentration lignin oxidations liquid.
Fig. 2 is the adsorbance of aromatic aldehyde in lignin oxidation's liquid under different temperatures.
Embodiment
Below in conjunction with specific embodiment further illustrate the present invention technical solution, these embodiments it is not intended that
It is the limitation to technical scheme.
The percentage sign " % " being related in the present invention, if not specified, refers to mass percent；But the percentage of solution,
Unless otherwise specified, refer to contain some grams of solute in solution 100ml；Percentage between liquid, refers to the capacity at 20 DEG C
Ratio.
Embodiment 1：Adsorbing separation is carried out to aromatic aldehyde according to following steps
（1）The preparation of lignin oxidation's liquid：Corncob acid hydrolytic residue add stainless steel cauldron in, add NaOH and
CuSO4, it is 10%, catalyst CuSO to make NaOH concentration4Concentration is 2%, is passed through oxygen 1.0MPa, speed of agitator 100rpm, is warming up to
160 DEG C, room temperature is cooled to after being kept for 180 minutes, 10% sulfuric acid adjusts reacting liquid pH value to 5, obtains lignin oxidation's liquid；
（2）Attapulgite adsorbing separation aromatic aldehyde：Attapulgite calcination in 500 DEG C of Muffle furnaces is cooled to room after 4 hours
Temperature；Liquid-solid ratio 50 is pressed again:1 is added to attapulgite in lignin oxidation's liquid, is placed in shaking table, and 200r/min, 30 DEG C of concussions are inhaled
Filtered after attached 1min, take filter cake；Filter cake mixes with 95% ethanol solution and is placed in shaking table, 200r/min, 30 DEG C of concussion desorption 10min
After filter, filtrate is fragrant aldehyde mixture.
Using high performance liquid chromatography（HPLC）Component analysis is carried out to lignin oxidation's liquid and eluent respectively and suction is calculated
Attached amount.Fig. 1 is the adsorbance of aromatic aldehyde in different initial concentration lignin oxidations liquid, it can be seen that fragrant aldehyde concentration is higher, recessed
Convex rod soil is bigger to its adsorbance, speculates that absorption of the aromatic aldehyde on attapulgite is possible for multi-molecular absorption accordingly.Together
When can be seen that attapulgite is maximum to the adsorbance of parahydroxyben-zaldehyde, this may have with the highly polar of parahydroxyben-zaldehyde
Close.Fig. 2 is the adsorbance of aromatic aldehyde in lignin oxidation's liquid under different temperatures, it can be seen that 30 DEG C are optimal adsorption temperature.
Embodiment 2：Adsorbing separation is carried out to aromatic aldehyde according to following steps
（1）The preparation of lignin oxidation's liquid：Factor of Enzymolysis Corn Stalk residue is added in stainless steel cauldron, adds NaOH
And CuSO4, it is 5%, catalyst CuSO to make NaOH concentration4Concentration is 0.5%, is passed through oxygen 0.5MPa, speed of agitator 300rpm, is risen
Temperature is cooled to room temperature to 200 DEG C after being kept for 60 minutes, 10% hydrochloric acid adjusts reacting liquid pH value to 6, obtains lignin oxidation's liquid；
（2）Attapulgite adsorbing separation aromatic aldehyde：Attapulgite calcination in 700 DEG C of Muffle furnaces is cooled to room after 4 hours
Temperature；Liquid-solid ratio 100 is pressed again:1 is added to attapulgite in lignin oxidation's liquid, is placed in shaking table, and 200r/min, 30 DEG C of concussions are inhaled
Filtered after attached 10min, take filter cake；Filter cake mixes with 95% ethanol solution and is placed in shaking table, 200r/min, 30 DEG C of concussion desorption 60min
After filter, filtrate is fragrant aldehyde mixture.
Embodiment 3：Adsorbing separation is carried out to aromatic aldehyde according to following steps
（1）The preparation of lignin oxidation's liquid：Wheat straw waste acid hydrolytic residue is added in stainless steel cauldron, adds NaOH
And CuSO4, it is 8%, catalyst CuSO to make NaOH concentration4Concentration is 1%, is passed through oxygen 0.8MPa, speed of agitator 200rpm, heating
To 180 DEG C, room temperature is cooled to after being kept for 120 minutes, 10% phosphoric acid adjusts reacting liquid pH value to 5.5, obtains lignin oxidation's liquid；
（2）Attapulgite adsorbing separation aromatic aldehyde：Attapulgite calcination in 600 DEG C of Muffle furnaces is cooled to room after 4 hours
Temperature；Liquid-solid ratio 75 is pressed again:1 is added to attapulgite in lignin oxidation's liquid, is placed in shaking table, and 200r/min, 30 DEG C of concussions are inhaled
Filtered after attached 5min, take filter cake；Filter cake mixes with 95% ethanol solution and is placed in shaking table, 200r/min, 30 DEG C of concussion desorption 30min
After filter, filtrate is fragrant aldehyde mixture.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, some improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (3)
1. the method for aromatic aldehyde adsorbing separation in lignin oxidation's liquid, using the lignocellulosic rich in lignin as raw material, through wet
After method catalytic oxidation, lignin oxidation's liquid is prepared；Lignin oxidation liquid pH is adjusted to slant acidity, then using attapulgite
Aromatic aldehyde compound in adsorbing separation lignin oxidation liquid；Finally use aromatic aldehyde chemical combination of the eluant, eluent absorption on attapulgite
Thing is eluted, and realizes Aromatic aldehyde compound from the initial gross separation in catalytic lignin oxidative breakdown product；It is characterized in that：Its
In, wet method catalytic oxidation condition is：Concentration of lye in 160 ~ 200 DEG C of temperature, 0.5 ~ 1.0MPa of oxygen pressure, reaction system
For 5 ~ 10%, catalyst 0.5 ~ 2%, 60 ~ 180min of reaction time, 100 ~ 300rpm of speed of agitator；Wherein, attapulgite absorption point
From operating procedure be：Lignin oxidation's liquid filtering, takes filtrate, regulation filtrate pH value to 5 ~ 6；Attapulgite is in 500 ~ 700 DEG C
Calcination is cooled to room temperature in Muffle furnace after 4 hours, then by liquid-solid ratio 50 ~ 100:Attapulgite is added to lignin oxidation's liquid by 1
In, filtered after being placed in shaking table, 200r/min, 30 DEG C of 1 ~ 10min of concussion absorption, take filter cake；Filter cake and the ethanol of mass concentration 95% are molten
Liquid mixing is filtered after being placed in shaking table, 200r/min, 30 DEG C of 10 ~ 60min of concussion desorption, and filtrate is fragrant aldehyde mixture.
2. the method for aromatic aldehyde adsorbing separation in lignin oxidation's liquid according to claim 1, it is characterized in that：Wherein, it is rich
Lignocellulosic material containing lignin is one kind in corncob, maize straw or wheat straw waste hydrolytic residue, its main group
It is divided into lignin.
3. the method for aromatic aldehyde adsorbing separation in lignin oxidation's liquid according to claim 1, it is characterized in that：Wherein, adjust
It is one kind in sulfuric acid, hydrochloric acid or phosphoric acid to save the acid used in lignin oxidation's liquid pH value, and mass concentration is 10%.
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