CN101628871B - Device for continuously converting glycerine into lactic acid by using hydrothermal reaction - Google Patents
Device for continuously converting glycerine into lactic acid by using hydrothermal reaction Download PDFInfo
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- CN101628871B CN101628871B CN 200910056559 CN200910056559A CN101628871B CN 101628871 B CN101628871 B CN 101628871B CN 200910056559 CN200910056559 CN 200910056559 CN 200910056559 A CN200910056559 A CN 200910056559A CN 101628871 B CN101628871 B CN 101628871B
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Abstract
The invention relates to a device for continuously converting glycerine into lactic acid by using hydrothermal reaction under alkaline condition, being composed of a high pressure metering pump (2), a pressure stabilizing system, a hydrothermal reaction system, a cooler (14), a tube type filter (18), and a back pressure valve (19). The mixed liquid of 0.33mol/L of glycerine and 1.25mol/L of alkaline are fed into the hydrothermal reaction system by the high pressure metering pump (2), the hydrothermal condition of 300 DEG C and 10MPa is maintained under the co-action of hydrothermal reaction system, pressure stabilizing system and back pressure valve, and 83% glycerine continuous conversion rate and more than 60% lactic acid continuous generation rate can be stably obtained in 60min. Compared with using a reaction kettle, the invention realizes continuous conversion reaction from glycerine into lactic acid with reasonable design and simple operation, and can realize recycle of lactic acid in match with acid neutralization and separation treatment. The invention can be widely used for producing glycerine, the cheap side product of bio-diesel industry into lactic acid with higher industrial value, thus realizing utilization of waste and expansion of bio-diesel industry chain.
Description
Technical field
The present invention relates to a kind of hydro-thermal reaction of utilizing glycerine be converted into the device of lactic acid continuously, specifically be adopt hydro-thermal reaction with the biological diesel oil byproduct raw glycerine as raw material, hydrothermal conversion is the continuous apparatus of lactic acid, belongs to chemical plant and changing waste into resources technical field.
Background technology
At present; Fossil energy be tending towards exhausted and situation that problem of environmental pollution is increasingly serious under; Biofuel more and more receives the concern of countries in the world as a kind of novel energy sustainable, neutral carbon, and overwhelming majority of countries has all been formulated the plan that significantly improves the biofuel usage ratio.With biofuel scale operation, main by-product glycerin is accumulation in a large number also.Raw glycerine is worth not high, and it is to produce soup and soap that tradition is utilized scheme, but can not solve current so over capacity; Raw glycerine also can be used for burn heat production and generating, but Yin Wendu need be difficult for promoting the use of above 1,000 ℃; At present some other the scheme of utilizing is also studied, and like system ethanol, system methyl alcohol, hydrogen manufacturing and Ucar 35 etc., mainly all is bioprocess, and conversion rate is slow, production efficiency is low and be difficult to realize industriallization, and these technology are also all immature.
The hydro-thermal reaction method is that nearly twenty or thirty rises over year and becomes one of focus of applied chemistry rapidly; It make full use of high-temperature water (comprise supercritical water and temperature that temperature, pressure are higher than 374.15 ℃ of stagnation point, 10MPa be higher than 200 ℃ but be lower than 374.15 ℃ liquid water) characteristic; As lower specific inductivity (is similar to the organic solvent under the normal temperature; Thereby organism and gas there are bigger solubleness even dissolve each other); The strong polarity of individual molecule (promote polarity/ionic reaction) and changeable ionic product (can be higher than 2-3 one magnitude under the normality, the reaction of promotion acid-base catalysis and need not to add in addition soda acid), and than high mass transfer efficiency; Realize material fast, the conversion of efficient, cleaning, be widely used aspect the biomass chemistry and the energy especially.Utilize hydrothermal method; Jin Fangming and Kishida H. etc. are lactic acid with transformation of glycerol fast and efficiently; And the mechanism of this reaction proposed according to product analysis; The latter also inquires into the kinetics of this reaction based on this reaction mechanism, and has inquired into reaction parameter, has drawn the conclusion of dynamics simulation result and sequence batch (experimental data basically identical.As everyone knows, lactic acid is higher, the increasing Chemicals of demand aborning of a kind of commercial value; The more important thing is that lactic acid is a kind of neutral carbon, be easy to the raw material of biodegradable vegetalitas plastics, day by day under the serious situation and receive much concern, therefore, transformation of glycerol has broad application prospects for the lactic acid process this plastics in current Global Greenhouse Effect.
At present, hydrothermal conversion glycerine is that lactic acid still rests on laboratory stage, and conversion process mainly realizes through intermittent reaction.The following usually operation of rhythmic reaction process: the aqueous solution of a certain amount of glycerine and alkali is injected the intermittent reaction pipe; Need then to purge remaining space in the reaction tubes with rare gas element; Tighten the salt bath of putting into preheating behind the reaction tubes, the concussion mixed reactant, anticipation reaction is after the time; Reaction tubes is put into the rapid cooling of cooling bath calm down reaction, open the reaction tubes sampling then.This process operation is loaded down with trivial details, and because the restriction of reaction conditions, single reaction tubes finite volume can't be realized producing in batches; Whole process consumes more manpower, and because human factor, lactic acid yield is unstable.Therefore, the production of batch is difficult to realize.
Summary of the invention
The objective of the invention is to disclose and a kind of glycerine is converted into the continuous apparatus of lactic acid fast, in the hope of generating the lactic acid small serial production for the glycerine hydro-thermal and equipment is provided, and then provide support for the industriallization of this reaction the serialization research of this reaction.
In order to achieve the above object; Sequence batch (experimental result based on Jin Fangming etc. designs, has developed this hydro-thermal reaction device continuously with the theoretical result of being obtained; And utilize it to realize lactic acid small serial production and serialization production research, inquire into the technological design and the operating parameter of Large Scale and Continuous equipment.
The present invention includes anchor, with the fixed high-pressure metering pump of the platform of anchor, voltage-stabilizing system, hydro-thermal reaction system, through the fixed water cooler of the top board of water cooler fixed link and anchor and blow-off valve, pipe filter, back pressure valve; Voltage-stabilizing system comprises water intaking valve, deoscillator, voltage-stabilizing system tensimeter and cooling cylinder; The hydro-thermal reaction system is by the salt bathtub, and the reaction tubes in the salt bathtub, heating rod, thermopair and stirrer are formed;
The import of high-pressure metering pump is connected with the sample introduction container; The high pressure measurement pump outlet is connected with voltage stabilizing threeway import through sampling valve; The reaction tubes with the hydro-thermal reaction system is connected in two outlets of voltage stabilizing threeway, and reaction tubes is connected with the cooling tube of water cooler, and cooling tube is connected with the emptying threeway with the reacting system pressure table respectively; Emptying threeway one end is connected with blow-off valve; The other end is connected with pipe filter, and pipe filter links to each other with the back pressure valve import, and the back pressure valve outlet is connected to the resultant container through one section stainless steel tube; Another of voltage stabilizing threeway is connected with the interior spiral coil cooling tube of the cooling cylinder of voltage-stabilizing system, and the spiral coil cooling tube outlet is connected with water intaking valve with deoscillator;
Above-mentioned cooling cylinder is placed on the platform of anchor, and the spiral coil cooling tube in the cooling cylinder is fixed with the cooling tube anchor; The spiral coil cooling tube anchor is made up of with 8 upright union levers of fixing these two annulus iron plates two horizontal circular ring iron plates up and down; 8 upright union levers are distributed on the circle of different diameter successively; 4 on big circumference; 4 on small circumference, every upright union lever two is fixed through nut and annulus iron plate respectively; Spiral coil cooling tube is coiled in 8 upright union levers and is fixed between the big small circumference; The cooling tube anchor immerses in the capacity cold water that holds in the cooling cylinder fully.
The salt bathtub of above-mentioned hydro-thermal reaction system is placed on the anchor platform; Reaction tubes in the salt bathtub is fixed on the reaction tubes anchor; Be immersed in fully in the mixing salt, be similar to the spiral coil cooling tube anchor, the reaction tubes anchor also is made up of with 8 upright union levers of fixing these two annulus iron plates two horizontal circular ring iron plates up and down; 8 upright union levers are distributed on the circle of different diameter successively; 4 on big circumference, 4 on small circumference, every upright union lever two is fixed through nut and annulus iron plate respectively; Reaction tubes is coiled in 8 upright union levers and is fixed between the big small circumference, and the reaction tubes anchor is immersed in the mixing salt fully.Hold weight ratio in the salt bathtub and be 1: 1 saltpetre and SODIUMNITRATE mixing salt; Salt bathtub center is provided with the blade fixed with the rotating shaft of stirrer; The circular hole that the reservation of anchor top board is passed in the rotating shaft of stirrer links to each other with the phonomoter of stirrer; Stirrer is fixed through union lever and support, and the top board of support and anchor is fixed.
The said fixing frame is by 4 upright angle steel with 4 levels rectangular parallelepiped that is welded; For the high temp. salt bathtub of avoiding placing on it scorches ground, 50 centimeters places of built on stilts, anchor bottom are becoming a platform with 4 horizontal corner steels with original 4 axial angle steel welding productions again; From security consideration, anchor top end face and front end face seal with iron sheet.
The concrete advantage applies of the present invention is in the following aspects:
1. because device of the present invention is provided with high-pressure metering pump; And back pressure valve and voltage-stabilizing system, make that the pressure in the hydro-thermal reaction system is stabilized in any pressure values between the 6-20MPa, almost can eliminate the pressure surge that forms by high-pressure metering pump fully; Utilize the alkaline water heat condition of this 300 ℃ of device formation, 10MPa; Reactant is imported in the reaction tubes of this device continuously to react, and generates continuously at the terminal lactic acid of device, has realized that continuous glycerine converting generates the purpose of lactic acid.
2. generate lactic acid because device of the present invention can stably be realized glycerine converting, therefore, can avoid dissolving in of gas to greatest extent, do not have gas in the reaction tubes, significantly reduce even eliminated the influence of gas this reaction; And the intermittent type device need add reactant in reaction tubes, brings air easily into, and the part outside the filling ratio needs other gas to fill (such as, N
2).
Since the whole process of device of the present invention by power operation; Avoided some to cause the unsettled human factor of lactic acid production rate; Like the addition that comes the accurate quantification reactant by volume pump, replace artificial concussion with the fluidised form mixed reactant and mix etc.; Thereby the production rate of lactic acid is stable.
4. the present invention has replaced hand feed with high-pressure metering pump, and product can flow directly into the resultant container, has saved the process of sampling one by one, has saved manpower greatly; When using existing intermittent type device in addition; Each reaction tubes is accomplished primary first-order equation just needs assembly and disassembly to accomplish charging and discharging; So frequent operation causes the stopping property variation, and a reaction tubes can only use several times just to be scrapped, and the present invention's use is a long reaction tubes; Stablely do not need frequent assembly and disassembly, thereby avoid such loss.
5. this device is easy to use, and can realize stablizing, hydrothermal condition widely.Only need to regulate temperature controller and can realize any temperature between 250-350 ℃; By deoscillator, can realize any pressure values between the 6-20MPa through regulating back pressure valve, the pressure surge in the reaction tubes has almost entirely been eliminated in being used of back pressure valve and gasbag-type deoscillator, and this is that intermittent apparatus can't be accomplished; In addition, through adjusting high pressure measurement pumping capacity, but the realization response time was from several minutes to several hours variation.
Description of drawings
Fig. 1 is a structural representation of the present invention.
Fig. 2 is a vertical view of the present invention.
Fig. 3 is an A-A sectional view of the present invention.
Fig. 4 is for to use the present invention with the lactic acid production rate graphic representation of glycerol liquor thermal transition as lactic acid.
Parts are followed successively by among the figure: 1-sample introduction container, 2-high-pressure metering pump, 3-sampling valve, 4-voltage stabilizing threeway, 5-water intaking valve, 6-deoscillator; 7-voltage-stabilizing system tensimeter, 8-cools off cylinder, 9-salt bathtub, 10-reaction tubes, 11-heating rod, 12-thermopair; The 13-stirrer, 14-water cooler, 15-reacting system pressure table, 16-emptying threeway, 17-blow-off valve; The 18-pipe filter, 19-back pressure valve, 20-resultant container, 21-anchor, 22-water cooler fixed link; 23-spiral coil cooling tube anchor, 24-reaction tubes anchor.
Embodiment
See also Fig. 1-4.
The present invention is the continuous hydrothermal conversion device that the biological diesel oil byproduct raw glycerine is converted into lactic acid, and its purpose realizes the main by product of biofuel exactly---the conversion and the utilization of raw glycerine.Glycerine is from Shanghai biofuel company, and biofuel is by microbial fermentation production, and glycerine is main by product.Raw glycerine is being plunderred removing dross, elimination impurity after acid-base neutralisation is adjusted to the glycerine solution of the about 10mg/L of glycerol content; Then add the NaOH solid to concentration 16.47mg/L; Insert in the sample introduction container 1 of continuous hydro-thermal reaction device of the present invention after making mixed solution; The import that sample introduction container 1 is received high-pressure metering pump 2 through a polyfluortetraethylene pipe, high-pressure metering pump 2 is fixedly mounted on the platform of anchor 21.High-pressure metering pump 2 outlets are connected with sampling valve 3, voltage stabilizing threeway 4 through stainless steel tube successively; In two outlets of voltage stabilizing threeway 4 one is connected with the reaction tubes 10 of hydro-thermal reaction system; Reaction tubes 10 is connected with the cooling tube of water cooler 14, and water cooler 14 two connect the mobile water coolant, and cooling tube is connected with emptying threeway 16 with reacting system pressure table 15 respectively; Emptying threeway 16 1 ends are connected with blow-off valve 17; The other end is connected with pipe filter 18, and pipe filter 18 links to each other with back pressure valve 19 imports, and back pressure valve 19 outlets are connected to resultant container 20 through one section stainless steel tube.
Apparatus of the present invention are connected into voltage-stabilizing system through voltage stabilizing threeway 4; The concrete connection is: another outlet of voltage stabilizing threeway 4 is connected with the cooling cylinder 8 interior spiral coil cooling tubes of voltage-stabilizing system; The spiral coil cooling tube outlet is connected with water intaking valve 5 with deoscillator 6; Mode of connection mainly adopts cutting ferrule and screw thread, and the core component of voltage-stabilizing system is a deoscillator 6, and deoscillator 6 adopts commercially available gasbag-type deoscillator.Cooling holds capacity cold water in the cylinder 8, the spiral coil cooling tube coiling be fixed on be immersed in fully in the cold water on spiral coil cooling tube anchor 23, pressure is shown by voltage-stabilizing system tensimeter 7.Cooling cylinder 8 is fixedly mounted on the platform of anchor 21.
The hydro-thermal reaction system is made up of salt bathtub 9, reaction tubes 10, heating rod 11, thermopair 12 and stirrer 13; Hold saltpetre and SODIUMNITRATE mixing salt (the amount of substance ratio is about 1: 1) in the salt bathtub 9; Reaction tubes 10 is by on the fixing reaction tubes anchor 24 that is immersed in fully in the mixing salt of coiling, and mixing salt is heated and presents molten when rod is heated to 250 ℃.Blow-off valve 17 is connected to emptying threeway 16 through stainless steel tube.Salt bathtub 9 is fixed on the platform of anchor 21; The blade of stirrer 13 places salt bathtub (9) center; Fixed with the rotating shaft of stirrer 13; The circular hole that the reservation of anchor 21 top boards is passed in the rotating shaft of stirrer links to each other with the phonomoter of stirrer, and stirrer is fixed through union lever and support, and the top board of support and anchor is fixed.
The two ends of water cooler 14 are fixed on the top board of anchor 21 with water cooler fixed link 22.
Whole piping system is except pump pipe connecting and strainer outer tube employing made in Great Britain 3/8 ", pipe, valve all are made in Great Britain 1/8 in the piping system ", the bite type joint is all adopted in the connection between the pipe valve.The stainless steel tube that contacts with reacting fluid, valve material are SUS316 (available from U.S. Swagelok company).
Principle of work:
Be contained in the glycerine of sample introduction container 1 and the aqueous solution of alkali, be input to reactor drum 10, in reactor drum 10, change into lactic acid by high-pressure metering pump 2.Mixing salt in the salt bathtub 9 can be heated to happy and harmonious state by heating rod 11; Temperature of reaction is by thermopair 12 controls; 13 in stirrer makes the melting salt temperature distribution consistent; Can be the reaction tubes 10 that immerses in the salt bath stable temperature is provided, this device can be realized any temperature value between 250-350 ℃.Reaction product is reduced to room temperature through supercooler 14, filters the back pressure valve 19 of flowing through again after 18 decons through the tubular type filter, flows into resultant container 20 at last.
The major function of back pressure valve 19 is the back pressures that in pipeline, form the reaction expection, can in reaction tubes 10, realize maximum 20MPa pressure through regulating back pressure valve 19.Because the compressibility of normal-temperature water and near-critical water is poor, huge pressure surge appears in the piping system that reciprocating type high-pressure metering pump 2 can cause, but by voltage-stabilizing system, this fluctuation almost completely is able to eliminate.The core component of voltage-stabilizing system is the gasbag-type deoscillator, utilizes the compressibility of the high pressure gas that the air bag in it charges into to come the intrasystem pressure surge of suction line, and finally can be reaction tubes provides between the 6-20MPa with stable pressure.It is the hydrothermal solution damage deoscillator 6 in order to prevent to flow backwards that pipeline section between deoscillator 6 and the voltage stabilizing threeway 4 is fixed in the cooling cylinder that holds capacity cold water.Blow-off valve 17 mainly is for can be when pipe filter 18 stops up the build-up of pressure abnormal conditions and occurs, or pipeline cleanings blowdown piping when needing, and 18 elimination large granular impurities before back pressure valve 19 of pipe filter prevent back pressure valve 19 obstructions.The installation of sampling valve 3 and water intaking valve 5 is convenient to piping system, inject reactant and deionized water from these two pipelines respectively.
The use flow process of this device is following:
At first, close sampling valve 3, open water intaking valve 5 and blow-off valve 17, inject deionized water from water intaking valve 3 to the voltage-stabilizing system pipeline, have deionized water to flow out until blow-off valve 17 with high-pressure metering pump 2.Afterwards, close water intaking valve 5, open sampling valve 3; Inject deionized water by the sample introduction pipeline to system with high-pressure metering pump 2; Wash whole pipeline, free from foreign meter in blow-off valve 17 effusive deionized waters, close blow-off valve 17 then; Regulate back pressure valve 19 simultaneously, make piping system pressure rise to preset value.At last, open the water coolant of water cooler 14, open heating rod 11 heating mixing salts, salt bath is stabilized in specified temperature through thermopair 12 and unit to molten state.
Treat that system pressure, temperature, flow reach specified condition; Deionized water is replaced to glycerine and the NaOH mixing solutions that designated ratio was taken off gas gradually; System stable operation (is longer than the reaction times more than 30 minutes) after for some time, after back pressure valve 19, can obtain to contain the solution of lactic acid (lactate ion).
The process of closing this device is following: at first stop salt bath being heated; Inject deionized water to piping system once more, treat that salt temperature reduces to normal temperature, close water coolant afterwards; Open blow-off valve 17 emptying; And strengthen the flow flushing pipeline of high-pressure metering pump 2 simultaneously, and enough low until reactant concn, close high-pressure metering pump 2 at last.
To the glycerine of certain concentration, in case conversion process stable after, this device can be realized the long-time continuous operation.Under the normal circumstances, do not need frequently must dismantle, clean.Cross long-play, change reactant concn and situation such as unusual such as higher occurs when pressure, when needing the dismounting pipe valve to clean, usually, must under this installs closing state, accomplish.
Claims (1)
1. with hydro-thermal reaction glycerine is converted into the device of lactic acid continuously, it is characterized in that: comprise anchor (21), with the fixed high-pressure metering pump (2) of the platform of anchor (21), voltage-stabilizing system, hydro-thermal reaction system with through the fixed water cooler (14) of the water cooler fixed link (22) and the top board of anchor (21) and blow-off valve (17), pipe filter (18), back pressure valve (19); Voltage-stabilizing system comprises water intaking valve (5), deoscillator (6), voltage-stabilizing system tensimeter (7) and cooling cylinder (8); The hydro-thermal reaction system is by salt bathtub (9), and the reaction tubes (10) in the salt bathtub (9), heating rod (11), thermopair (12) and stirrer (13) are formed;
The import of high-pressure metering pump (2) is connected with sample introduction container (1); The outlet of high-pressure metering pump (2) is connected with voltage stabilizing threeway (4) import through sampling valve (3); One is connected with the reaction tubes (10) of hydro-thermal reaction system in two outlets of voltage stabilizing threeway (4), and reaction tubes (10) is connected with the cooling tube of water cooler (14), and cooling tube is connected with emptying threeway (16) with reacting system pressure table (15) respectively; Emptying threeway (16) one ends are connected with blow-off valve (17); The other end is connected with pipe filter (18), and pipe filter (18) links to each other with back pressure valve (19) import, and back pressure valve (19) outlet is connected to resultant container (20) through one section stainless steel tube; Another of voltage stabilizing threeway (4) is connected with the interior spiral coil cooling tube of the cooling cylinder (8) of voltage-stabilizing system, and the spiral coil cooling tube outlet is connected with water intaking valve (5) with deoscillator (6);
Above-mentioned cooling cylinder (8) is placed on anchor (21) platform; Anchor is by 4 upright angle steel with 4 levels rectangular parallelepiped that is welded; For the high temp. salt bathtub of avoiding placing on it scorches ground, 50 centimeters places of built on stilts, anchor bottom are becoming a platform with 4 horizontal corner steels with original 4 axial angle steel welding productions again; From security consideration, anchor top end face and front end face seal with iron sheet;
Spiral coil cooling tube in the cooling cylinder (8) is fixing with spiral coil cooling tube anchor (23); Spiral coil cooling tube anchor (23) is made up of with 8 upright union levers of fixing these two annulus iron plates two horizontal circular ring iron plates up and down; 8 upright union levers are distributed on the circle of different diameter successively, 4 on big circumference, 4 on small circumference; Every upright union lever two is fixed through nut and annulus iron plate respectively; 8 upright union levers form two circumference of size, and spiral coil cooling tube is coiled between these two circumference, and spiral coil cooling tube anchor (23) immerses in the capacity cold water that holds in the cooling cylinder (8) fully;
The salt bathtub (9) of above-mentioned hydro-thermal reaction system is placed on anchor (21) platform; Reaction tubes (10) in the salt bathtub (9) is fixed on the reaction tubes anchor (24); Reaction tubes anchor (24) structure and spiral coil cooling tube anchor (23) are identical; The mode that reaction tubes (10) is fixed on the reaction tubes anchor (24) is identical with the mode that spiral coil cooling tube is fixed on spiral coil cooling tube anchor (23), and reaction tubes anchor (24) is immersed in the mixing salt fully, and the saltpetre and the SODIUMNITRATE that hold weight ratio in the salt bathtub (9) and be 1: 1 mix mixing salt; Salt bathtub (9) center is provided with the fixed blade of rotating shaft with stirrer (13); The circular hole that the reservation of anchor top board is passed in the rotating shaft of stirrer links to each other with the phonomoter of stirrer, and stirrer is fixed through union lever and support, and the top board of support and anchor is fixed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910056559 CN101628871B (en) | 2009-08-18 | 2009-08-18 | Device for continuously converting glycerine into lactic acid by using hydrothermal reaction |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200910056559 CN101628871B (en) | 2009-08-18 | 2009-08-18 | Device for continuously converting glycerine into lactic acid by using hydrothermal reaction |
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| CN101628871B true CN101628871B (en) | 2012-12-05 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914650B (en) * | 2010-06-29 | 2012-07-04 | 同济大学 | Method for reducing oxidation state iron into simple substance iron by using glycerol |
| CN101985104B (en) * | 2010-11-02 | 2012-11-28 | 长安大学 | Catalyst used for preparation of biodiesel by using swill-cooked dirty oil |
| US9447011B2 (en) | 2012-11-21 | 2016-09-20 | University Of Tennessee Research Foundation | Methods, systems and devices for simultaneous production of lactic acid and propylene glycol from glycerol |
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2009
- 2009-08-18 CN CN 200910056559 patent/CN101628871B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| F. Jin et al.."A NEW HYDROTHERMAL PROCESS FOR PRODUCING ACETIC ACID FROM BIOMASS WASTE".《Trans IChemE, Part A, Chemical Engineering Research and Design》.2007,第85卷(第A2期),第201-206页. |
| Fangming Jin et al.."Application of hydrothermal reaction to conversion of plant-origin biomasses into acetic and lactic acids".《J Mater Sci》.2007,第43卷(第7期),第2363-2471页. |
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