CN104357588B - One kind surpasses/subcritical water CO2The method that hydrolysis sugarcane marrow prepares reduced sugar - Google Patents
One kind surpasses/subcritical water CO2The method that hydrolysis sugarcane marrow prepares reduced sugar Download PDFInfo
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- CN104357588B CN104357588B CN201410619564.3A CN201410619564A CN104357588B CN 104357588 B CN104357588 B CN 104357588B CN 201410619564 A CN201410619564 A CN 201410619564A CN 104357588 B CN104357588 B CN 104357588B
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K11/00—Fructose
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K13/00—Sugars not otherwise provided for in this class
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K5/00—Lactose
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K7/00—Maltose
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Abstract
One kind surpasses/subcritical water CO2The method that hydrolysis sugarcane marrow prepares reduced sugar, step are：(1) sugarcane marrow and water are added into autoclave, and is filled with CO2Reacted, control temperature reacts 1~60min under conditions of 160~260 DEG C, 100~500r/min of 1~8MPa of pressure and speed of agitator, then by material press filtration in autoclave, takes the filtrate out, as reduced sugar, filter residue is stayed in autoclave；(2) have in step (1) in the autoclave of filter residue and be passed through water and CO2Continue to react, control temperature reacts 0~5min under conditions of 370~400 DEG C, 100~500r/min of 20~27MPa of pressure and speed of agitator, and then material in autoclave is cooled to after room temperature and carries out press filtration, gained filtrate is reduced sugar.The inventive method improves the yield of sugarcane marrow hydrolysis, and does not have solvent contamination, and without the postprocessing working procedures of complexity, and reaction rate is fast, yield is high, and reducing sugar yield can reach more than 90%.
Description
Technical field
The invention belongs to Green Chemistry and clean energy technology field, is related to a kind of super/subcritical water-CO2Hydrolyze sugarcane marrow
The method for preparing reduced sugar.
Background technology
Bagasse is the accessory substance of sugar enterprise, is mainly used as the raw material of papermaking, but therein 30% ~ 40% is sugarcane marrow（It is short
Fiber）, it is mainly used in boiler combustion, utilization rate is very low.It is cellulose that sugarcane marrow, which mainly forms, and cellulose is converted into clean fuel
Core technology is that cellulose is hydrolyzed into the soluble reducing sugars such as glucose using effective method.
CN201310319341.0 discloses hydrochloric acid hydrolysis-cellulase ultrasound enzymolysis cellulose and prepares the pre- of bio-ethanol
Processing method, realized by following steps：Biomass through crushing is placed in reactor, in 30-100 DEG C, soaked with HCl solution
2-120 hours are steeped, reacted material are evaporated under reduced pressure at 50-120 DEG C, redistillation 1-3 times after residue is mixed with water, then
Residue is adjusted into faintly acid addition cellulase with inorganic base to be well mixed, 2- is digested in 40-60 DEG C under ul-trasonic irradiation
60h, obtain the material containing reduced sugar.
CN201210170770.1, which is disclosed, is related to the Processes and apparatus that a kind of biologic enzymolysis method prepares reduced sugar, the equipment
Including：Enzyme mebrane reactor, have and be used to hold bagasse and cellulase buffer solution and complete the reaction inner bag of enzyme digestion reaction, and
For providing the water bath containers of water bath with thermostatic control for reaction inner bag, and the membrane module that reactor is adapted to is used for completing enzymolysis instead
The enzymolysis liquid answered is separated, and obtains reduced sugar and enzymolysis residue；Enzyme transfer device, for enzymolysis residue and new bagasse
Abundant contact and carry out enzyme heavily adsorb, the new reaction mass that new bagasse by enzyme heavily adsorb is formed is transferred to enzyme membrane by pipeline
The reaction inner bag of reactor completes enzyme digestion reaction；And the connecting pipe between each unit.The equipment causes in preparation technology also
Raw sugar is separated in time, improves enzymolysis efficiency, and the enzyme heavily adsorb of new substrate is carried out after digesting, and realizes the circulation profit of enzyme
With reducing enzymolysis cost.
CN200910072156.X discloses a kind of method of biomass for preparing fermentable reducing sugar, by the biological material of selection
Feed powder is broken, be screened into 60 mesh powder after, be placed in the beaker for filling finite concentration organic acid and be well mixed, and be put into micro-wave oven
In, 2~5min of radiation treatment under conditions of microwave power is 400~700W, products therefrom is filtered and is dried to constant weight.So
Cellulase solution is configured, is mixed with biomass, finally by three according to solid-to-liquid ratio 1: 10~1: 25, pH4 ~ 5 in triangular flask afterwards
The thermostat water bath that angle bottle is placed in 50~60 DEG C is hydrolyzed, and obtains reduced sugar
CN200910072867.7 discloses can the sugared side of fermentation reducing using ionic liquid processing cellulose biomass system
Method, different types of ionic liquid will be synthesized, and after the cellulose biomass of selection is ground into powder, it is molten by certain solid-to-liquid ratio
In ionic liquid, 30~180min is reacted in 120~150 DEG C under normal pressure, after reaction terminates, deionized water is added and is regenerated
Cellulose, separate and dry constant weight.According to certain solid-to-liquid ratio in triangular flask, cellulase solution is configured in pH4~5, with regeneration
Cellulose mixes, and is placed in 50~60 DEG C of thermostat water bath and is digested；Stoichiometric is carried out to content of reducing sugar in enzymolysis liquid
Analysis, the results showed that content of reducing sugar reaches as high as 42g/l.
In summary, these methods for preparing reduced sugar using cellulose are mainly acid or enzyme hydrolysis.Acid system dilute sulfuric acid
Higher reaction rate can be reached, have the percent hydrolysis effect for significantly improving cellulose, but acid has corrosivity, has to human body
Evil, need to be reacted in corrosion resistant reactor, require higher to reactor, and waste reaction solution has pollution, rear place to environment
It is complicated to manage step.Enzyme hydrolysis has the advantages that selectivity is good, reaction condition is gentle, environment-friendly, equipment is simple, but reaction time
It is long, and to prepare purification difficult, cost high for cellulase, still have from large-scale industrial production with a certain distance from.With ionic liquid
The method of body processing, the problem of product separation hardly possible, subsequent treatment complexity be present.In recent years, super/subcritical water using water as solvent
Grape berry cellulose turns into study hotspot.
The content of the invention
The present invention is directed to the deficiency of above-mentioned technology, invents a kind of super/subcritical water-CO2Hydrolysis sugarcane marrow prepares reduced sugar
Method, utilize super/subcritical water and CO2Coupling, sugarcane marrow is hydrolyzed and prepares reduced sugar, this method is green, reaction
Cycle is short, and reducing sugar yield is high, and technological process is more succinct.
To realize the purpose of the present invention, the present invention provides following technical scheme：
One kind surpasses/subcritical water-CO2The method that hydrolysis sugarcane marrow prepares reduced sugar, includes following operating procedure：
（1）Sugarcane marrow and water are added into autoclave, and are filled with CO2Reacted as auxiliary agent, control temperature is 160 ~ 260
DEG C, 1 ~ 60min is reacted under conditions of 100 ~ 500r/min of 1 ~ 8MPa of pressure and speed of agitator, then by material pressure in autoclave
Filter, takes the filtrate out, as reduced sugar, filter residue is stayed in autoclave；
（2）Step（1）In have in the autoclave of filter residue and be passed through water and CO2Continue to react in autoclave as auxiliary agent, control
Temperature processed reacts 3 ~ 5min under conditions of 370 ~ 400 DEG C, 100 ~ 500r/min of 20 ~ 27MPa of pressure and speed of agitator, then will
Material carries out press filtration after being cooled to room temperature in autoclave, and gained filtrate is reduced sugar.
Wherein, step（1）The sugarcane marrow of middle addition is with water quality than 1:20~1:100.
Wherein, step（2）The filter residue of middle addition is with water quality than 1:20~1:100.
Wherein, described water is distilled water or deionized water.
Compared with prior art, beneficial effects of the present invention：
Using super/subcritical water-CO2United hydrolysis sugarcane marrow prepares reduced sugar, is hydrolyzed equivalent to faintly acid, and hydrolytic process adds
Enter CO2The acidity of system can be improved, further promotes sour water solution, improves the yield of sugarcane marrow hydrolysis, and does not have solvent contamination,
Without the postprocessing working procedures of complexity, and reaction rate is fast, yield is high, and reducing sugar yield can reach more than 90%.And the original used
Material sugarcane marrow such as concentrated on sugar refinery in the production process of sucrose, be not required to collect and transport at the expense；Sugarcane marrow has crushed when squeezing sugared
For fine particle, it is not required to make pulverization process, the raw materials such as stalk, corncob is far below on production cost.Using the production of sucrose
The discarded object sugarcane marrow of journey is raw material, and this has Important Economic value and environment protection significance to the recycling for improving sugarcane marrow.
Embodiment
The present invention is further described referring to embodiment, to make those skilled in the art with reference to specification text
Word can be implemented according to this, and the scope of the present invention is not limited to embodiments of the present invention.Autoclave used in embodiment,
Static seal magnetic agitation is carried in kettle, is inserted with into and out of expects pipe and probe tube.In embodiment, subcritical water condition reaction is referred to as low
Temperature reaction, supercritical water state response are referred to as pyroreaction.
Embodiment 1
By sugarcane marrow and distilled water in mass ratio 1:20 add autoclave, are filled with 4MPa CO2It is anti-that low temperature is carried out as auxiliary agent
Should, controlling reaction temperature reacts 30min under conditions of 210 DEG C, reaction pressure 8MPa and speed of agitator 500r/min；Then it is straight
Connected discharge nozzle and press filtration is carried out to material in autoclave, took the filtrate out, as reduced sugar, gained reduced sugar yield is
26.6%, filter residue stays in and pyroreaction raw material is used as in autoclave, filter residue and distilled water in mass ratio 1:60 add water to high pressure
In kettle, 7MPa CO is filled with2Reacted as auxiliary agent, controlling reaction temperature is in 370 DEG C, pressure 24MPa and speed of agitator
3min is reacted under conditions of 500r/min；Autoclave reaction product is cooled to after room temperature and carries out press filtration, filtrate is containing also
The product of raw sugar, gained reduced sugar yield are 74.0%, sugarcane marrow reductive hydrolysis sugar gross production rate 80.9%.
Embodiment 2：
By sugarcane marrow and deionized water in mass ratio 1:60 add autoclave, are filled with 2MPa CO2Low temperature is carried out as auxiliary agent
Reaction, controlling reaction temperature react 60min under conditions of 260 DEG C, reaction pressure 5MPa and speed of agitator 300r/min；Then
Press filtration is directly carried out to material in autoclave by discharge nozzle, taken the filtrate out, as reduced sugar, gained reduced sugar yield is
23.7%, filter residue, which stays in, is used as pyroreaction raw material in autoclave, by filter residue and deionized water in mass ratio 1:20 add water to height
Press in kettle, be filled with 7MPa CO2Reacted as auxiliary agent, controlling reaction temperature is in 390 DEG C, pressure 26MPa and speed of agitator
5min is reacted under conditions of 300r/min；Autoclave reaction product is cooled to after room temperature and carries out press filtration, filtrate is containing also
The product of raw sugar, gained reduced sugar yield are 75.4%, sugarcane marrow reductive hydrolysis sugar gross production rate 81.2%.
Embodiment 3：
By sugarcane marrow and deionized water in mass ratio 1:100 add autoclave, and controlling reaction temperature is in 160 DEG C, reaction pressure
40min is reacted under conditions of power 1MPa and speed of agitator 100r/min；Then directly material in autoclave is entered by discharge nozzle
Row press filtration, takes the filtrate out, as reduced sugar, and gained reduced sugar yield is 20.7%, and filter residue stays in anti-as high temperature in autoclave
Raw material is answered, by filter residue and distilled water in mass ratio 1:100 add water in autoclave, are filled with 7MPa CO2Carried out as auxiliary agent
Reaction, controlling reaction temperature react 5min under conditions of 400 DEG C, pressure 27MPa and speed of agitator 100r/min；It will be produced in kettle
Thing carries out press filtration, and filtrate is the product containing reduced sugar, and gained reduced sugar yield is 76.0%, sugarcane marrow reductive hydrolysis sugar gross production rate
81.0%。
Embodiment 4：
With reference to the operating method of embodiment 3, change following parameter respectively：The ratio of sugarcane marrow and water, reaction temperature, reaction pressure
Power, reaction time, speed of agitator are carried out preparing reducing sugar reaction, drawn such as the data in table 1.
Table 1
In table 1, solid-to-liquid ratio is bagasse and the mass ratio of deionized water, and yield is gained reduced sugar yield, and each step is anti-
Yield summation obtained by reduced sugar is yield obtained by this method final reducing sugar after answering.By in table it can be seen that the inventive method with
Carbon dioxide is auxiliary agent, has very high yield in the reduced sugar prepared by super/subcritical water hydrolysis sugarcane marrow, total recovery is up to
More than 90%.
Using super/subcritical water-CO2United hydrolysis sugarcane marrow prepares reduced sugar, is hydrolyzed equivalent to faintly acid, and hydrolytic process adds
Enter CO2The acidity of system can be improved, further promotes sour water solution, improves the yield of sugarcane marrow hydrolysis, and does not have solvent contamination,
Without complicated postprocessing working procedures, and reaction rate is fast, yield is high, and reducing sugar yield can reach more than 90%.And the raw material used
Sugarcane marrow has concentrated on sugar refinery in the production process of sucrose, is not required to collect and the expense such as transports；Sugarcane marrow has crushed when squeezing sugared
Fine particle, it is not required to make pulverization process, the raw materials such as stalk, corncob is far below on production cost.Using the production process of sucrose
Discarded object sugarcane marrow be raw material, this to improve sugarcane marrow recycling have Important Economic be worth and environment protection significance, moreover, by entering
Row low-temp reaction is into high-temperature reaction process, it is not necessary to cools, directly using the discharge nozzle of autoclave by reduced sugar in autoclave
Take out, so that need not further be heated during pyroreaction, greatly reduce energy consumption.
Claims (2)
1. one kind surpasses/subcritical water-CO2The method that hydrolysis sugarcane marrow prepares reduced sugar, it is characterised in that include following operating procedure：
（1）Sugarcane marrow and water are added into autoclave, and are filled with CO2Reacted, control temperature 190 ~ 200 DEG C, 7 ~ 8MPa of pressure and
1 ~ 60min is reacted under conditions of 100 ~ 500r/min of speed of agitator, then by material press filtration in autoclave, is taken the filtrate out, i.e.,
For reduced sugar, filter residue is stayed in autoclave；The sugarcane marrow of addition is with water quality than 1:20~1:60；
（2）Step（1）In have in the autoclave of filter residue and be passed through water and CO2Continue to react, control temperature is in 375 ~ 380 DEG C, pressure 20
3 ~ 5min is reacted under conditions of 100 ~ 500r/min of ~ 27MPa and speed of agitator, after material in autoclave then is cooled into room temperature
Press filtration is carried out, gained filtrate is reduced sugar；The filter residue of addition is with water quality than 1:50.
2. surpass/subcritical water-CO according to claim 12The method that hydrolysis sugarcane marrow prepares reduced sugar, it is characterised in that：It is described
Water be distilled water or deionized water.
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| WO2011091044A1 (en) * | 2010-01-19 | 2011-07-28 | Sriya Innovations, Inc. | Production of fermentable sugars and lignin from biomass using supercritical fluids |
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