CN106317134B - A kind of method that hydro-thermal method hydrolysis tannin extract prepares glucose and gallic acid - Google Patents
A kind of method that hydro-thermal method hydrolysis tannin extract prepares glucose and gallic acid Download PDFInfo
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- CN106317134B CN106317134B CN201610700987.7A CN201610700987A CN106317134B CN 106317134 B CN106317134 B CN 106317134B CN 201610700987 A CN201610700987 A CN 201610700987A CN 106317134 B CN106317134 B CN 106317134B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/02—Monosaccharides
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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
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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Abstract
The invention discloses the method that a kind of hydro-thermal method hydrolysis tannin extract prepares glucose and gallic acid, step includes：(1) using hydro-thermal method, for pressure for 0.1~2.8MPa, temperature hydrolyzes 0.5~2.0h of tannin extract under the conditions of being 120~240 DEG C in high-temperature high-pressure reaction kettle, and filtering or centrifugation obtain hydrolyzate；(2) using clarification limewash neutralizing hydrolysis liquid, precipitation is generated, filtering or centrifugation obtain solution and precipitation；(3) solution is concentrated is spray-dried up to glucose；(4) precipitation is acidified using dilution heat of sulfuric acid, then uses CaCO3Or it is 4.0~6.0 that clarification limewash, which adjusts souring soln pH, the solution that filtering or centrifugation obtain is concentrated to be spray-dried up to gallic acid.The present invention is using water as solvent under high-temperature and high-pressure conditions, and environmentally friendly, efficient, obtained glucose and gallic acid has higher economic value, can effectively improve the added value of tannin extract.
Description
Technical field
The present invention relates to the methods that a kind of hydro-thermal method hydrolysis tannin extract prepares chemicals, are hydrolyzed more particularly to a kind of hydro-thermal method
The method that tannin extract prepares glucose and gallic acid, belongs to field of chemical engineering.
Background technology
Tannin extract is a kind of important tanning agent, and mainly tanning uses in leather industry.In addition, also serve as beneficiation inhibitor,
Water treating agent for boilers, drilling mud diluent, metal surface corrosion inhibitor and adhesive.It is by the plant material warp rich in tannin
Hot water extraction, concentration and drying and other steps processing chemical products obtained.The main component of tannin extract is tannin, according to its structure
Tannin can be divided into Hydrolysable Tannins and condensed tannin by difference, and wherein Hydrolysable Tannins refers to being derived by gallic acid or gallic acid
The ester that is formed of phenol carboxylic acid and polyalcohol (such as glucose), be widely present in acorn cup, change in fragrant fruit and Chinese gall.In recent years,
In order to open up tannin extract application new way and improve tannin extract higher value application, researcher is prepared for tannin extract by chemical modification
Some high added value materials, and its technology of preparing patent is disclosed, such as phenol formaldehyde foam is prepared using tannin extract
(CN201210575450.4), the additive (CN01130562.2) of adhesive (CN95103379.4) and adhesive, these hairs
Bright patent is all based on the modification of tannin extract polyhydric phenols structure and prepares its high molecular material, and using tannin extract prepare the patent of chemicals compared with
It is few.
Hydro-thermal method refers in the pressure vessel of sealing, and using water as solvent, the chemistry carried out under conditions of high temperature and pressure is anti-
It answers.The technology has been widely used in the chemical processes such as hydrolysis, redox, crystalline deposit.According to hydro-thermal reaction
The difference of process condition, can be classified as subcritical and supercritical reaction, wherein subcritical reaction temperature 100~240 DEG C it
Between, it is suitable for industrialized production, and supercritical reaction temperature is up to thousands of degree, pressure is up to 0.3Gpa, severe reaction conditions.And it goes
In the industry traditional tannin extract method for hydrolysis be using dilute sulfuric acid or dilute hydrochloric acid processing tannin extract, pollute environment, and to equipment corrosion compared with
Greatly, the present invention is exactly environmental pollution and equipment etching problem caused by order to solve above-mentioned sour water solution.Currently, having no using hydro-thermal
Method hydrolysis tannin extract prepares related patents and its research of glucose and gallic acid.
This patent prepares glucose and gallic acid using hydro-thermal method hydrolysis acorn cup, the fragrant fruit of change and Chinese gall tannin extract, former
Reason is that water forms H under high-temperature and high-pressure conditions+, to the ester of gallic acid in hydrolysable tannins in this tannin extracts and glucose formation
Key is hydrolyzed, and then glucose and gallic acid is prepared.Glucose has extensive and important in medicine food field
Purposes, gallic acid are a kind of important industrial chemicals, also referred to as gallic acid or gallate, chemical name 3,4,5- trihydroxies
Benzoic acid has a wide range of applications in food medicine and biological chemical field.Currently, in the market tannin extract price be 10000 yuan/
Ton, and industrial glucose price be 72000 yuan/ton, gallic acid price be 70000 yuan/ton, it can be seen that, this patent with
Tannin extract is raw material, and the glucose and gallic acid of high added value are prepared using hydro-thermal method hydrolysis tannin extract, can effectively improve tannin extract
Higher value application has huge potential age deduction.
Invention content
Environmental pollution and equipment etching problem, provide one kind caused by the purpose of the invention is to overcome sour water solution tannin extract
The method that hydro-thermal method hydrolysis tannin extract prepares glucose and gallic acid, the technology belong to field of chemical engineering.
The purpose of the present invention is achieved through the following technical solutions：
A kind of method that hydro-thermal method hydrolysis tannin extract prepares glucose and gallic acid, includes the following steps：
(1) mass volume ratio of tannin extract and water is 1:10~1:25, in high-temperature high-pressure reaction kettle pressure be 0.1~
2.8MPa, temperature are stirred to react 0.5~2.0h under the conditions of being 120~240 DEG C, and reaction solution is cooled to room temperature, the list of the quality
Position is kg, and the unit of the volume is L；
(2) step (1) reaction solution is filtered or is centrifuged；
(3) step (2) filtered fluid or centrifugate clarification limewash are neutralized, generates precipitation, filtering or centrifugation, obtains
To solution and precipitation；
(4) step (3) described solution is concentrated by evaporation to 30~40%；
(5) step (4) concentrate is spray-dried, obtains glucose；
(6) step (3) described precipitation is acidified with dilution heat of sulfuric acid, then uses CaCO3Or clarification limewash adjusting acidification is molten
Liquid pH is 4.0~6.0, filtering or centrifugation；
(7) step (6) filtered fluid or centrifugate are concentrated by evaporation to 30~40%；
(8) step (7) concentrate is spray-dried, obtains gallic acid.
To further realize the object of the invention, the tannin extract described in step (1) is acorn cup, changes and appoint in fragrant fruit and Chinese gall tannin extract
What is a kind of.
Step (2), step (3) and step (6) described centrifugal rotational speed be 1000~5000rpm/min, centrifugation time be 5~
20min。
Step (4) and step (7) it is described be concentrated by evaporation be system of three-effect downstream evaporator concentrate, one effect pressure be 0.05~
1.0MPa, 100~110 DEG C of temperature, a concentration of 5~8%, two effect pressure be 0MPa, 100~110 DEG C of temperature, a concentration of 20~
25%, triple effect -0.004~-0.005MPa of pressure, temperature be 100~110 DEG C, a concentration of 30~40%.
Step (6) a concentration of 0.1~1.0M of the dilution heat of sulfuric acid.
Spray drying described in step (5) and step (8) is pressure spray dryer, centrifugal spray drying, air-flowing type spraying
Any one in drying.
Advantageous effect
It has not yet to see any use hydro-thermal method hydrolysis tannin extract and prepares glucose and gallic acid technical patent and research public affairs
It opens, the present invention is using water as solvent under high-temperature and high-pressure conditions, and environmental protection, efficiently, and obtained glucose and gallic acid have
Higher economic value.
Description of the drawings
Attached drawing 1 is that hydro-thermal method hydrolysis tannin extract prepares glucose and gallic acid process flow diagram.
Specific implementation mode
With reference to embodiment and attached drawing, invention is described in further detail, but embodiments of the present invention are not limited to
This.
Embodiment 1
The method that the present embodiment hydro-thermal method hydrolysis tannin extract prepares glucose and gallic acid, includes the following steps：
(1) valonea extract 1kg is weighed, is added in 10L water, is stirred to react under the conditions of 120 DEG C of temperature, pressure 0.1Mpa
0.5h, reaction solution are cooled to room temperature；
(2) step (1) reaction solution is filtered；
(3) step (2) filtered fluid clarification limewash is neutralized, generates precipitation, filtering obtains solution and precipitation；
(4) step (3) described filtered fluid is concentrated into 30% using system of three-effect downstream evaporator；
(5) use centrifugal spray drying up to glucose, yield 10%, purity 75% step (4) described concentrate；
(6) step (3) the precipitation 0.1M dilution heat of sulfuric acid is acidified, then uses CaCO3Adjusting souring soln pH is
4.0, filtering；
(7) step (6) described filtered fluid is concentrated into 30% using system of three-effect downstream evaporator；
(8) step (7) described concentrate is used into pressure spray dryer, obtains gallic acid, yield 18%, purity
85%.
Embodiment 2
The method that the present embodiment hydro-thermal method hydrolysis tannin extract prepares glucose and gallic acid, includes the following steps：
(1) the fragrant fruit tannin extract 1kg of weighing, is added in 25L water, is stirred under the conditions of 240 DEG C of temperature, pressure 2.8Mpa anti-
2.0h, reaction solution is answered to be cooled to room temperature；
(2) step (1) described reaction solution is centrifuged into 20min at rotating speed 1000rpm/min；
(3) step (2) the centrifugate clarification limewash of crossing is neutralized, precipitation is generated, at rotating speed 1000rpm/min
20min is centrifuged, solution and precipitation are obtained；
(4) step (3) described centrifugate is concentrated into 40% using system of three-effect downstream evaporator；
(5) use pressure spray dryer up to glucose, yield 8%, purity 70% step (4) described concentrate；
(6) step (3) the precipitation 1.0M dilution heat of sulfuric acid is acidified, then souring soln pH is adjusted with clarification limewash
It is 6.0,20min is centrifuged at rotating speed 1000rpm/min；
(7) step (6) described filtrate is concentrated into 40% using system of three-effect downstream evaporator；
(8) step (7) described concentrate is used into pneumatic spray drying, obtains gallic acid, yield 20%, purity
90%.
Embodiment 3
The method that the present embodiment hydro-thermal method hydrolysis tannin extract prepares glucose and gallic acid, includes the following steps：
(1) Chinese gall tannin extract 1kg is weighed, is added in 20L water, is stirred under the conditions of 140 DEG C of temperature, pressure 0.5Mpa anti-
1.0h, reaction solution is answered to be cooled to room temperature；
(2) step (1) described reaction solution is centrifuged into 5min at rotating speed 5000rpm/min；
(3) step (2) the centrifugate clarification limewash of crossing is neutralized, precipitation is generated, at rotating speed 5000rpm/min
5min is centrifuged, solution and precipitation are obtained；
(4) step (3) described centrifugate is concentrated into 32% using system of three-effect downstream evaporator；
(5) use pneumatic spray drying up to glucose, yield 12%, purity 80% step (4) described concentrate；
(6) step (3) the precipitation 0.5M dilution heat of sulfuric acid is acidified, then uses CaCO3Adjusting souring soln pH is
5.0, centrifuge 5min at rotating speed 5000rpm/min；
(7) step (6) described centrifugate is concentrated into 33% using system of three-effect downstream evaporator；
(8) step (7) described concentrate is used into centrifugal spray drying, obtains gallic acid, yield 22%, purity
92%.
Embodiment 4
The method that the present embodiment hydro-thermal method hydrolysis tannin extract prepares glucose and gallic acid, includes the following steps：
(1) valonea extract 1kg is weighed, is added in 15L water, is stirred to react under the conditions of 160 DEG C of temperature, pressure 1.0Mpa
1.5h, reaction solution are cooled to room temperature；
(2) step (1) reaction solution is filtered；
(3) step (2) filtered fluid clarification limewash is neutralized, generates precipitation, at rotating speed 3000rpm/min from
Heart 10min, obtains solution and precipitation；
(4) step (3) described centrifugate is concentrated into 36% using system of three-effect downstream evaporator；
(5) use centrifugal spray drying up to glucose, yield 15%, purity 85% step (4) described concentrate；
(6) step (3) the precipitation 0.3M dilution heat of sulfuric acid is acidified, then souring soln is adjusted with clarification limewash
PH is 5.5, filtering；
(7) step (6) described filtrate is concentrated into 34% using system of three-effect downstream evaporator；
(8) step (7) described concentrate is used into centrifugal spray drying, obtains gallic acid, yield 24%, purity
93%.
Embodiment 5
The method that the present embodiment hydro-thermal method hydrolysis tannin extract prepares glucose and gallic acid, includes the following steps：
(1) Chinese gall tannin extract 1kg is weighed, is added in 18L water, is stirred under the conditions of 200 DEG C of temperature, pressure 1.5Mpa anti-
1.2h, reaction solution is answered to be cooled to room temperature；
(2) step (1) described reaction solution is centrifuged into 15min at rotating speed 2500rpm/min；
(3) step (2) centrifugate clarification limewash is neutralized, generates precipitation, filtering obtains solution and precipitation；
(4) step (3) described filtered fluid is concentrated into 38% using system of three-effect downstream evaporator；
(5) use pneumatic spray drying up to glucose, yield 14%, purity 87% step (4) described concentrate；
(6) step (3) the precipitation 0.8M dilution heat of sulfuric acid is acidified, then uses CaCO3Adjusting souring soln pH is
12min is centrifuged under 4.5, rotating speed 1500rpm/min；
(7) step (6) described filtrate is concentrated into 37% using system of three-effect downstream evaporator；
(8) step (7) described concentrate is used into pressure spray dryer, obtains gallic acid, yield 25%, purity
94%.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features,
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention's
Within protection domain.
Claims (6)
1. a kind of method that hydro-thermal method hydrolysis tannin extract prepares glucose and gallic acid, which is characterized in that include the following steps：
(1) mass volume ratio of tannin extract and water is 1:10~1:25, pressure is 0.1~2.8MPa in high-temperature high-pressure reaction kettle,
Temperature is stirred to react 0.5~2.0h under the conditions of being 120~240 DEG C, and reaction solution is cooled to room temperature, and the unit of the quality is kg,
The unit of the volume is L；
(2) step (1) reaction solution is filtered or is centrifuged；
(3) step (2) filtered fluid or centrifugate clarification limewash are neutralized, generates precipitation, filtering or centrifugation, obtains molten
Liquid and precipitation；
(4) step (3) described solution is concentrated by evaporation to 30~40%；
(5) step (4) concentrate is spray-dried, obtains glucose；
(6) step (3) described precipitation is acidified with dilution heat of sulfuric acid, then uses CaCO3Or clarification limewash adjusting souring soln pH is
4.0~6.0, it filters or centrifuges；
(7) step (6) filtered fluid or centrifugate are concentrated by evaporation to 30~40%；
(8) step (7) concentrate is spray-dried, obtains gallic acid.
2. the method that hydro-thermal method hydrolysis tannin extract according to claim 1 prepares glucose and gallic acid, which is characterized in that
Tannin extract described in step (1) is acorn cup, changes any type in fragrant fruit and Chinese gall tannin extract.
3. the method that hydro-thermal method hydrolysis tannin extract according to claim 1 prepares glucose and gallic acid, which is characterized in that
Step (2), step (3) and step (6) described centrifugal rotational speed are 1000~5000rpm/min, and centrifugation time is 5~20min.
4. the method that hydro-thermal method hydrolysis tannin extract according to claim 1 prepares glucose and gallic acid, which is characterized in that
Step (4) and described be concentrated by evaporation of step (7) are that system of three-effect downstream evaporator concentrates, and an effect pressure is 0.05~1.0MPa, temperature 100
~110 DEG C, a concentration of 5~8%, two effect pressure be 0MPa, 100~110 DEG C of temperature, a concentration of 20~25%, triple effect pressure-
0.004~-0.005MPa, temperature be 100~110 DEG C, a concentration of 30~40%.
5. the method that hydro-thermal method hydrolysis tannin extract according to claim 1 prepares glucose and gallic acid, which is characterized in that
Step (6) a concentration of 0.1~1.0M of the dilution heat of sulfuric acid.
6. the method that hydro-thermal method hydrolysis tannin extract according to claim 1 prepares glucose and gallic acid, which is characterized in that
Spray drying described in step (5) and step (8) is in pressure spray dryer, centrifugal spray drying, pneumatic spray drying
Any one.
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| CN111454143A (en) * | 2020-05-13 | 2020-07-28 | 遵义市倍缘化工有限责任公司 | Method for preparing gallic acid by hydrolyzing sulfuric acid capable of utilizing by-product |
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| CN1706790A (en) * | 2005-05-09 | 2005-12-14 | 竹山县天新医药化工有限责任公司 | Gallic acid producing process |
| CN101161628A (en) * | 2007-11-15 | 2008-04-16 | 浙江大学 | Method for preparing gallic acid and pyrogallic acid synchronously by non-catalyzed hydrolysis of tannin-containing biomass in high-temperature liquid water medium |
| CN102977548A (en) * | 2012-12-27 | 2013-03-20 | 北京莱恩斯高新技术有限公司 | Vegetable tannin extract modified phenol formaldehyde foam and preparation method thereof |
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2016
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|---|---|---|---|---|
| CN1117986A (en) * | 1995-05-07 | 1996-03-06 | 柴万知 | Method for producing tannin-extract adhesive |
| CN1422928A (en) * | 2001-12-02 | 2003-06-11 | 杨文章 | Additive of applying condensed tannin extracts as adhesive for thermosetting wood |
| CN1706790A (en) * | 2005-05-09 | 2005-12-14 | 竹山县天新医药化工有限责任公司 | Gallic acid producing process |
| CN101161628A (en) * | 2007-11-15 | 2008-04-16 | 浙江大学 | Method for preparing gallic acid and pyrogallic acid synchronously by non-catalyzed hydrolysis of tannin-containing biomass in high-temperature liquid water medium |
| CN102977548A (en) * | 2012-12-27 | 2013-03-20 | 北京莱恩斯高新技术有限公司 | Vegetable tannin extract modified phenol formaldehyde foam and preparation method thereof |
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