CN103149318A - Method for quantitatively analyzing acetylpropionic acid in biomass liquefaction product - Google Patents
Method for quantitatively analyzing acetylpropionic acid in biomass liquefaction product Download PDFInfo
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Abstract
The invention relates to a method for quantitatively analyzing a liquefaction product, and especially relates to a method for quantitatively analyzing acetylpropionic acid in a biomass liquefaction product. The method comprises the following steps: making a linear equation of the sample application amount of acetylpropionic acid and SKS, applying a solution to be detected on a silica gel plate, and carrying out scanning and data acquisition, and carrying out signal separating analysis of the acquired data through the combination of an oblique projection operator to complete the quantitative analysis of the detected component acetylpropionic acid in the solution of the biomass liquefaction product. There is no need to develop each of solutions to be detected in a developing solvent, so the cost is saving; the acquired date are abundant, so the quantitative analysis error is small, and the analysis is convenient and fast; and the method has the advantages of simple and rapid operation, accuracy and good reappearance of the result, overcoming of the thin layer chromatogram semi-quantitative analysis disadvantage, and simultaneous suitableness for the analysis, the production process monitoring, the product quality control and the like of a batch of acetylpropionic acid samples, and is a new analysis method for the quantitative analysis of acetylpropionic acid.
Description
Technical field
The present invention relates to a kind of quantitative analysis method of liquefaction products, the particularly quantitative analysis method of laevulic acid in a kind of biomass liquefying product.
Background technology
Laevulic acid is a kind of novel green hardware and software platform compound, and its assay method has vanillic aldehyde-sulfuric acid process, vapor-phase chromatography, thin layer chromatography scanning, the chromatography of ions, high performance liquid chromatography at present.
Vanillic aldehyde-sulfuric acid process is to utilize laevulic acid in sulfuric acid medium, and under the abundant oxidizing condition of potassium dichromate, with vanillic aldehyde, react at a certain temperature, and present different colors, the depth of color is relevant with the content of laevulic acid, the method can estimate the content of laevulic acid in the biomass liquefying product to a certain extent, but troublesome poeration, standard color range are only stable at short notice.
The Gas Chromatographic Method of laevulic acid has direct method and indirect method two classes at present, indirect method is first by the laevulic acid esterification, then uses gas chromatographic analysis, but this method complex operation, and easily produce error in preprocessing process, thereby affect the accuracy of result; And direct method has result characteristics accurate, simple to operate, but high to equipment requirement, analysis time is long, analysis cost is high.High performance liquid chromatography can analyze the various compositions in product, but also exist,, analysis time high to equipment requirement is long, analysis cost is higher.
Adopt the thin layer scanning of single wavelength or dual wavelength to collect the data message amount less, caused the quantitative test error larger, and measured object need to be separated it fully with developping agent from compounding substances for single wavelength or dual-wavelength lamellar scanning quantitative test, make that the thin layer quantitative test is consuming time, consumptive material, can not its content of Accurate Determining.
Summary of the invention
The technical problem to be solved in the present invention is: provide that a kind of accuracy is high, cost is low, the conveniently quantitative analysis method of laevulic acid in the biomass liquefying product.
The technical scheme solved the problems of the technologies described above is: the quantitative analysis method of laevulic acid in a kind of biomass liquefying product comprises the following steps;
A. make the linear equation of laevulic acid point sample amount and SKS value:
A1. prepare the laevulic acid standard solution: laevulic acid is mixed with to variable concentrations a
1, a
2, a
3... a
ythe laevulic acid standard solution;
A2. obtain the spectroscopic data of laevulic acid: by the laevulic acid standard solution of the variable concentrations for preparing in steps A 1 respectively point sample on silica gel plate, use up slim layer scanner scanning, gather the spectroscopic data of laevulic acid;
A3. translation data form: the spectroscopic data of the laevulic acid that collects in above-mentioned steps A2 is become to the KS function data by the light intensity data format conversion;
A4. the SKS value of suing for peace to obtain: by the summation of the KS value under each wavelength of gained in steps A 3, obtain the SKS value;
A5. make the linear equation of laevulic acid point sample amount and SKS value: according to point sample amount and the SKS value of laevulic acid, make the point sample amount of laevulic acid and the linear equation of SKS value; This linear equation is y=ax+b, and wherein, x is the point sample amount, and y is the SKS value, and a and b are constant;
B. the mensuration of levulinic acid content in liquefaction products:
B1. obtain the spectroscopic data M of liquefaction products: the liquefaction products point sample, on silica gel plate, is used up to slim layer scanner scanning, and the light intensity data that scanning is obtained converts the KS function data to, obtains spectroscopic data M;
B2. obtain spectroscopic data W and spectroscopic data Z: liquefaction products and laevulic acid are distinguished to point sample on silica gel plate, after developping agent launches, use up the spot that slim layer scanner scans respectively liquefaction products and laevulic acid expansion, convert the light intensity data of scanning collection to the KS function data, obtain the spectroscopic data of liquefaction products and laevulic acid, to the KS data mapping be converted to, obtain the thin-layer chromatography separation characteristic figure of liquefaction products and laevulic acid, thin-layer chromatography separation characteristic figure chosen spectrum data W in the spectroscopic data of liquefaction products according to laevulic acid, other spectroscopic datas after deduction spectroscopic data W are spectroscopic data Z,
B3. the number of principal components N's of liquefaction products is definite: to the spectroscopic data Z in step B2, the application principal component analysis (PCA) is determined the number of principal components N of liquefaction products;
B4. obtain the spectroscopic data S of laevulic acid in liquefaction products: according to the number of principal components N of the liquefaction products obtained in step B3, choose liquefaction products in the spectroscopic data W obtained at step B2 in the spectroscopic data S of laevulic acid;
B5. background extraction spectroscopic data H: after the application svd is done dimension-reduction treatment to the spectroscopic data Z obtained in step B2, according to the number of principal components N of the liquefaction products obtained in step B3, select background spectrum data H;
B6. calculate the SKS value of laevulic acid in liquefaction products: in conjunction with the oblique projection operator, the data that gather are carried out to the signal compartment analysis, the background spectrum data H of gained in the spectroscopic data S of gained in the spectroscopic data M of gained in step B1 and step B4 and step B5 is imported in oblique projection Operators Algorithm program, calculate the SKS value of laevulic acid in liquefaction products;
B7. calculate the content of laevulic acid in liquefaction products: the content of laevulic acid in liquefaction products will be tried to achieve in the linear equation of the point sample amount of resulting laevulic acid in the SKS value substitution steps A of laevulic acid in the liquefaction products obtained in step B6 and SKS value.
Further technical scheme of the present invention is: described in steps A 1, prepare the laevulic acid standard solution for laevulic acid is mixed with to variable concentrations a
1, a
2, a
3, a
4, a
5the laevulic acid standard solution.
Developping agent described in step B2 is: after sodium bicarbonate solution and ethyl acetate are mixed, take out upper solution, the solution of taking-up and methyl alcohol are obtained by mixing to developping agent.
The separation characteristic of the thin-layer chromatography according to laevulic acid figure described in step B2 step of chosen spectrum data W and spectroscopic data Z in the scan-data of liquefaction products is: the position of determining the spectroscopic data of laevulic acid on the thin-layer chromatography separation characteristic figure of laevulic acid, position according to the spectroscopic data of laevulic acid, select the data of relevant position as spectroscopic data W in the spectroscopic data of liquefaction products, the data after deduction spectroscopic data W are as spectroscopic data Z.
Principal component analysis (PCA) described in step B3 is judgement system independent variable counting method.
The step of the spectroscopic data S that obtains laevulic acid in liquefaction products described in step B4 is: according to the number of principal components N of the liquefaction products obtained in step B3, the middle N column data in spectroscopic data W is selected to the spectroscopic data S of laevulic acid in liquefaction products.
The step of background extraction spectroscopic data H described in step B5 is: application svd [U, S, V]=svd (Z) does dimension-reduction treatment to spectroscopic data Z, decompose and obtain data U, S, V, according to the number of principal components N of the liquefaction products according to obtaining in step B3, the front N column selection in data U is gone out to spectroscopic data H as a setting.
The switch process of described KS function is: application KS=(ones (sizeab)-Refe) .^2./(2*Refe) is become spectroscopic data the data layout of KS functional form by the Data Format Transform of light intensity, wherein, the reflective light intensity data of Refe for adopting the optical fiber thin-layer chromatogram scanner to gather; Sizeab is the dimension from the data of the reflective light intensity data acquisition that gathers according to the absorbing wavelength of tested component; It is 1 matrix that ones helps the reflective light intensity data-switching of collection according to the absorbing wavelength scope.
Oblique projection operator described in step B6 is E
s|H=S (S
tp
h ⊥s)
-1s
tp
h ⊥, P
h ⊥=I-P
h=I-H (H
th)
-1h
t, wherein, subscript T represents transpose of a matrix; I is and P
hthe unit matrix that dimension is identical; E
s|Hfor the oblique projection operator; The subspace that the vector that S is measured variable is opened; The adjacent subspace of H for not opening containing the vector of measured variable; P
hfor the projection operator along subspace H to subspace S.
Owing to adopting technique scheme, in a kind of biomass liquefying product of the present invention, the quantitative analysis method of laevulic acid is compared with existing quantitative analysis method, has following beneficial effect:
1. accuracy is high:
The present invention only need carry out the biomass liquefying product thin-layer developing and separate, and obtain the correlation computations data, when analyzing by the liquefaction products point sample on silica gel plate, directly adopt the optical fiber thin-layer chromatogram scanner to gather optical fiber thin layer scanning data, in conjunction with the oblique projection operator, the data that gather are carried out to the signal compartment analysis, can complete the quantitative test of laevulic acid in liquefaction products.The data volume gathered is abundant, and the quantitative test error is little, and accuracy is high.
2. cost is low, convenient and swift:
The present invention adopts the optical fiber thin-layer chromatogram scanner directly to carry out the scanning collection data to biomass liquefying product solution point sample on silica gel plate, the spectroscopic data collected is done to principal component analysis (PCA) and svd processing, and then by the data computing to obtain the content of tested component laevulic acid in solution to be measured, the present invention only need carry out the biomass liquefying product thin-layer developing and separate, having solved needs in the classic method that the tested component in potpourri is separated to rear ability fully and measured matter is carried out to the problem of thin layer scanning quantitative test, the data that record are accurate than the result of the tlc analysis of classic method, this method is convenient for the thin layer quantitative test simultaneously, fast, the present invention has shortened analysis time, saved cost.
Method simple, be convenient to promote the use of:
The present invention first prepares the point sample amount of laevulic acid and the linear equation of SKS with the laevulic acid standard solution of variable concentrations, select spectroscopic data and the background spectrum data of measured object from data according to thin-layer chromatography separation characteristic figure, the solution to be measured on silica gel plate directly carries out the scanning collection data to point sample to use up slim layer scanner again, carry out the quantitative test that the data computing completes tested component laevulic acid in biomass liquefying product solution, without the long complex operations of process, the present invention can be for the fast quantitative analysis of laevulic acid solution, method is simple, easy to operate, be convenient to promote the use of.
Below, the technical characterictic in conjunction with Figure of description and specific embodiment to the quantitative analysis method of laevulic acid in a kind of biomass liquefying product of the present invention is further described.
the accompanying drawing explanation:
Fig. 1: flow chart of steps of the present invention.
Fig. 2: the spectrogram of the laevulic acid in the present embodiment,
Horizontal ordinate in Fig. 2 means that wavelength (nm), ordinate mean the KS value.
Fig. 3: the thin-layer chromatography separation characteristic figure of liquefaction products,
Horizontal ordinate in Fig. 3 means that spacing (mm), ordinate mean the KS value,
In Fig. 3, each label is: the chromatographic peak of 1-laevulic acid.
Fig. 4: the thin-layer chromatography separation characteristic figure of laevulic acid,
Horizontal ordinate in Fig. 4 means that spacing (mm), ordinate mean the KS value,
In Fig. 4, each label is: the chromatographic peak of 2-laevulic acid.
Fig. 5: number of principal components and second order difference value variation diagram,
Horizontal ordinate in Fig. 5 means that number of principal components, ordinate mean the second order difference value.
embodiment:
In a kind of biomass liquefying product, the quantitative analysis method of laevulic acid, comprise the following steps;
A. make the linear equation of laevulic acid point sample amount and SKS value:
A1. prepare the laevulic acid standard solution:
A11. accurately take laevulic acid 0.1000g, move in the 100mL volumetric flask after dissolving with distilled water, use the distilled water constant volume, the laevulic acid mother liquor that to be mixed with concentration be 1.0g/L.
A12. accurately pipette respectively laevulic acid mother liquor 1.0mL, 4.0mL, 6.0mL, 8.0mL, 10.0mL and be placed in the 10mL volumetric flask, use the distilled water constant volume, the laevulic acid standard solution that to be mixed with concentration be 0.1g/L, 0.4g/L, 0.6g/L, 0.8g/L, 1.0g/L.
A2. obtain the spectroscopic data of laevulic acid:
A21. prepare the optical fiber thin-layer chromatogram scanner: this optical fiber thin-layer chromatogram scanner comprises light source, fibre-optical probe, spectrometer, electric displacement platform, optical fiber, and the parameter that the optical fiber thin-layer chromatogram scanner is set is: the spectrum integral time is that 50ms, average time are 6, scanning integration interval time 300ms, sweep velocity are 200step/s.
A22. with the microsyringe laevulic acid standard solution 20uL point sample that the concentration of gained is 0.1g/L, 0.4g/L, 0.6g/L, 0.8g/L, 1.0g/L in removing step A12 respectively on G type high-efficient silica gel plate, dry and form the point sample spot, optical fiber thin-layer chromatogram scanner fibre-optical probe is placed on the point sample spot and carries out " bow " shape two-dimensional movement mode and scan, obtain the spectroscopic data of laevulic acid, determine the absorbing wavelength scope, referring to Fig. 2.
Wherein, above-mentioned to use up some data in the data that slim layer scanner scanning obtain are clear datas, according to wavelength coverage, can in scan-data, select needed data, and data volume makes calculated amount reduce with regard to minimizing like this.
A3. translation data form:
The data layout that the spectroscopic data gathered in above-mentioned steps A2 is light intensity, application KS=(ones (sizeab)-Refe) .^2./(2*Refe) converts the spectroscopic data of the laevulic acid that gathers in steps A 22 to the data layout of KS functional form, obtains the KS value of laevulic acid.
In described KS=(ones (sizeab)-Refe) .^2./(2*Refe): the reflective light intensity data of Refe for adopting the optical fiber thin-layer chromatogram scanner to gather; Sizeab is the dimension from the data of the reflective light intensity data acquisition that gathers according to the absorbing wavelength of tested component; It is 1 matrix that ones helps the reflective light intensity data-switching of collection according to the absorbing wavelength scope.
A4. the SKS value of suing for peace to obtain:
Application sum (sum (KS)) tries to achieve the SKS value of laevulic acid point sample spot, and soon in steps A 3, the KS value of the laevulic acid under each wavelength of gained is sued for peace, and tries to achieve the SKS value of the point sample amount of each point sample spot of laevulic acid, referring to table 1.
A5. make the linear equation of laevulic acid point sample amount and SKS value:
Make the point sample amount of laevulic acid and the linear equation of SKS value according to point sample amount and the SKS value of laevulic acid; This linear equation is y=ax+b, and wherein, x is the point sample amount, and y is the SKS value, and a and b are constant, referring to table 1.
B. the mensuration of levulinic acid content in liquefaction products:
B1. obtain the spectroscopic data M of liquefaction products:
For the effect of the quantitative test of the quantitative analysis method that adopts in can more effective explanation the present invention, the liquefaction products in the present embodiment is for preparing voluntarily by the following method the liquefaction products obtained:
B11. the preparation of liquefaction products I: by scoot under 80 ℃ dry 2 hours, through comminutor, pulverize, take the 2.0g wood chip in three-neck flask, the hydrochloric acid 100mL and the 5.4g catalyzer ferric trichloride that add 6.3mol/L by liquid-solid ratio (mL/g) 50:1, at 103 ℃ of lower magnetic force stirring reaction 4.5h, will react the liquefaction products of 4.5h with standby as the liquefaction products I after the ultrafiltration membrance filter of 0.45 μ m.
B12. the preparation of liquefaction products II: by scoot under 80 ℃ dry 2 hours, through comminutor, pulverize, take the 2.0g wood chip in three-neck flask, the hydrochloric acid 100mL and the 5.4g catalyzer ferric trichloride that add 6.3mol/L by liquid-solid ratio (mL/g) 50:1, at 103 ℃ of lower magnetic force stirring reaction 6.0h, will react the liquefaction products of 6.0h with standby as the liquefaction products II after the ultrafiltration membrance filter of 0.45 μ m.
B13. obtaining of the spectroscopic data of liquefaction products I and liquefaction products II: the above-mentioned liquefaction products I prepared and liquefaction products II are pipetted respectively to the 20uL point sample on G type high-efficient silica gel plate with microsyringe, parallel point sample three times, dry and form the point sample spot, point sample spot on G type high-efficient silica gel plate is placed under the fibre-optical probe of optical fiber thin-layer chromatogram scanner, set sweep parameter, with fibre-optical probe, the point sample spot is carried out to the scanning of " bow " type, preserve the data of scanning collection, by the market demand KS=(ones (sizeab) that preserves-Refe) .^2./(2*Refe) data-switching of light intensity the is become data of KS function, data after conversion are as the spectroscopic data of liquefaction products, obtain the spectroscopic data M of liquefaction products I after conversion
ithe spectroscopic data M of (I=1,2,3), liquefaction products II
iI(II=4,5,6).
B2. obtain spectroscopic data W and spectroscopic data Z:
B21. the laevulic acid mother liquor 20 μ L point samples that to get respectively liquefaction products II and concentration be 1.00g/L are on silica gel plate, launch 15min in developping agent, taking-up is dried, use up the spot that slim layer scanner scans respectively liquefaction products II and laevulic acid expansion, convert the light intensity data of scanning collection to the KS functional form, obtain the spectroscopic data of liquefaction products II and laevulic acid, to the mapping of KS data, obtain the thin-layer chromatography separation characteristic figure (as shown in Figure 3, Figure 4) of liquefaction products II and laevulic acid.According to the chromatographic peak position of laevulic acid, select the data of correspondence position as spectroscopic data W in the spectroscopic data of liquefaction products II, other spectroscopic datas of deduction spectroscopic data W are as spectroscopic data Z.Described developping agent is for after respectively getting sodium bicarbonate solution that 100mL concentration is 0.10mol/L and ethyl acetate and being placed in separating funnel and mixing, by separating funnel at the middle and upper levels solution take out, the upper solution of taking-up and methyl alcohol are obtained by mixing for 5:1 by volume.
B3. the number of principal components N's of liquefaction products is definite:
The thin-layer chromatography separation characteristic figure obtained from step B2 can find out that the composition of liquefaction products is comparatively complicated, and the data volume of spectroscopic data Z is larger, therefore before calculating, need spectroscopic data Z is made to principal component analysis (PCA) and svd processing, the background spectrum data that judgement is selected according to number of principal components and the columns of measured object laevulic acid spectroscopic data.
Adopt judgement system independent variable counting method to determine the system number of principal components, determine number of principal components according to the variation of second order difference value, the spectroscopic data Z of gained in step B21 mapping is obtained to number of principal components and second order difference value variation diagram (as Fig. 5), in Fig. 5, " break " comes across the position that sequence number is 5, after this second order difference value variation is comparatively smooth, therefore judgement liquefaction products number of principal components is 5.
B4. obtain the spectroscopic data S of laevulic acid in liquefaction products:
According to the number of principal components 5 of the liquefaction products obtained in step B3, centre 5 column datas in the spectroscopic data W obtained in step B21 are selected to the spectroscopic data S of laevulic acid in liquefaction products.
B5. background extraction spectroscopic data H:
B51. the spectroscopic data Z obtained in step B21 is not for containing the data of measured object laevulic acid, and this data volume is large, causes calculated amount very large.Simply need to carry out the svd dimension-reduction treatment to data for making to calculate, application [U, S, V]=svd (Z) carries out the svd dimensionality reduction to spectroscopic data Z, obtains data U, S, V, and wherein, svd is svd.
B52. according to the number of principal components 5 of the liquefaction products obtained in step B3, front 5 column selections by data U that obtain in step B51 are gone out to spectroscopic data H as a setting.
B6. calculate the SKS value of laevulic acid in liquefaction products:
B61. calculate the SKS value of laevulic acid in the liquefaction products I: by the spectroscopic data M of the liquefaction products I of gained in step B13
ibring with the spectroscopic data S of laevulic acid in the liquefaction products of gained in the background spectrum data H of gained in step B52 and step B4 the SKS value of obtaining laevulic acid in the liquefaction products I in oblique projection Operators Algorithm program into.
B62. calculate the SKS value of laevulic acid in the liquefaction products II: by the spectroscopic data M of the liquefaction products II of gained in step B13
iIbring with the spectroscopic data S of laevulic acid in the liquefaction products of gained in the background spectrum data H of gained in step B52 and step B4 the SKS value of obtaining laevulic acid in the liquefaction products II in oblique projection Operators Algorithm program into.
Oblique projection operator described above is E
s|H=S (S
tp
h ⊥s)
-1s
tp
h ⊥, P
h ⊥=I-P
h=I-H (H
th)
-1h
t, wherein, subscript T represents transpose of a matrix; I is and P
hthe unit matrix that dimension is identical; E
s|Hfor the oblique projection operator; The subspace that the vector that S is measured variable is opened; The adjacent subspace of H for not opening containing the vector of measured variable; P
hfor the projection operator along subspace H to subspace S.
B7. calculate the content of laevulic acid in liquefaction products:
B71. calculate the content of laevulic acid in the liquefaction products I: the SKS value of laevulic acid in the liquefaction products I calculated in step B61 is brought in the linear equation y=ax+b of the point sample amount of the laevulic acid obtained in steps A 5 and SKS value, calculate the content of laevulic acid in the liquefaction products I, referring to table 2.
B72. calculate the content of laevulic acid in the liquefaction products II: the SKS value of laevulic acid in the liquefaction products II calculated in step B61 is brought in the linear equation y=ax+b of the point sample amount of the laevulic acid obtained in steps A 5 and SKS value, calculate the content of laevulic acid in the liquefaction products II, referring to table 2.
The point sample amount of table 1 laevulic acid and the linear equation of SKS value
The measurement result of laevulic acid in table 2 liquefaction products
A kind of conversion as the present embodiment: also can get the liquefaction products of liquefaction products I as expanded sweep in step B21.
Claims (9)
1. the quantitative analysis method of laevulic acid in a biomass liquefying product, is characterized in that: comprise the following steps;
A. make the linear equation of laevulic acid point sample amount and SKS value:
A1. prepare the laevulic acid standard solution: laevulic acid is mixed with to variable concentrations a
1, a
2, a
3... a
ythe laevulic acid standard solution;
A2. obtain the spectroscopic data of laevulic acid: by the laevulic acid standard solution of the variable concentrations for preparing in steps A 1 respectively point sample on silica gel plate, use up slim layer scanner scanning, gather the spectroscopic data of laevulic acid;
A3. translation data form: the spectroscopic data of the laevulic acid that collects in above-mentioned steps A2 is become to the KS function data by the light intensity data format conversion;
A4. the SKS value of suing for peace to obtain: by the summation of the KS value under each wavelength of gained in steps A 3, obtain the SKS value;
A5. make the linear equation of laevulic acid point sample amount and SKS value: according to point sample amount and the SKS value of laevulic acid, make the point sample amount of laevulic acid and the linear equation of SKS value; This linear equation is y=ax+b, and wherein, x is the point sample amount, and y is the SKS value, and a and b are constant;
B. the mensuration of levulinic acid content in liquefaction products:
B1. obtain the spectroscopic data M of liquefaction products: the liquefaction products point sample, on silica gel plate, is used up to slim layer scanner scanning, and the light intensity data that scanning is obtained converts the KS function data to, obtains spectroscopic data M;
B2. obtain spectroscopic data W and spectroscopic data Z: liquefaction products and laevulic acid are distinguished to point sample on silica gel plate, after developping agent launches, use up the spot that slim layer scanner scans respectively liquefaction products and laevulic acid expansion, convert the light intensity data of scanning collection to the KS function data, obtain the spectroscopic data of liquefaction products and laevulic acid, to the KS data mapping be converted to, obtain the thin-layer chromatography separation characteristic figure of liquefaction products and laevulic acid, thin-layer chromatography separation characteristic figure chosen spectrum data W in the spectroscopic data of liquefaction products according to laevulic acid, other spectroscopic datas after deduction spectroscopic data W are spectroscopic data Z,
B3. the number of principal components N's of liquefaction products is definite: to the spectroscopic data Z in step B2, the application principal component analysis (PCA) is determined the number of principal components N of liquefaction products;
B4. obtain the spectroscopic data S of laevulic acid in liquefaction products: according to the number of principal components N of the liquefaction products obtained in step B3, choose liquefaction products in the spectroscopic data W obtained at step B2 in the spectroscopic data S of laevulic acid;
B5. background extraction spectroscopic data H: after the application svd is done dimension-reduction treatment to the spectroscopic data Z obtained in step B2, according to the number of principal components N of the liquefaction products obtained in step B3, select background spectrum data H;
B6. calculate the SKS value of laevulic acid in liquefaction products: in conjunction with the oblique projection operator, the data that gather are carried out to the signal compartment analysis, the background spectrum data H of gained in the spectroscopic data S of gained in the spectroscopic data M of gained in step B1 and step B4 and step B5 is imported in oblique projection Operators Algorithm program, calculate the SKS value of laevulic acid in liquefaction products;
B7. calculate the content of laevulic acid in liquefaction products: the content of laevulic acid in liquefaction products will be tried to achieve in the linear equation of the point sample amount of resulting laevulic acid in the SKS value substitution steps A of laevulic acid in the liquefaction products obtained in step B6 and SKS value.
2. the quantitative analysis method of laevulic acid in a kind of biomass liquefying product according to claim 1 is characterized in that: described in steps A 1, prepare the laevulic acid standard solution for laevulic acid is mixed with to variable concentrations a
1, a
2, a
3, a
4, a
5the laevulic acid standard solution.
3. the quantitative analysis method of laevulic acid in a kind of biomass liquefying product according to claim 1, it is characterized in that: the developping agent described in step B2 is: after sodium bicarbonate solution and ethyl acetate are mixed, take out upper solution, the solution of taking-up and methyl alcohol are obtained by mixing to developping agent.
4. the quantitative analysis method of laevulic acid in a kind of biomass liquefying product according to claim 3, it is characterized in that: the step of chosen spectrum data W and spectroscopic data Z in the scan-data of liquefaction products of the separation characteristic of the thin-layer chromatography according to the laevulic acid figure described in step B2 is: the position of determining the spectroscopic data of laevulic acid on the thin-layer chromatography separation characteristic figure of laevulic acid, position according to the spectroscopic data of laevulic acid, select the data of relevant position as spectroscopic data W in the spectroscopic data of liquefaction products, data after deduction spectroscopic data W are as spectroscopic data Z.
5. the quantitative analysis method of laevulic acid in a kind of biomass liquefying product according to claim 1 is characterized in that: the principal component analysis (PCA) described in step B3 is judgement system independent variable counting method.
6. the quantitative analysis method of laevulic acid in a kind of biomass liquefying product according to claim 5, it is characterized in that: the step of the spectroscopic data S that obtains laevulic acid in liquefaction products described in step B4 is: according to the number of principal components N of the liquefaction products obtained in step B3, the middle N column data in spectroscopic data W is selected to the spectroscopic data S of laevulic acid in liquefaction products.
7. the quantitative analysis method of laevulic acid in a kind of biomass liquefying product according to claim 5, it is characterized in that: the step of the background extraction spectroscopic data H described in step B5 is: application svd [U, S, V]=svd (Z) does dimension-reduction treatment to spectroscopic data Z, decompose and obtain data U, S, V, according to the number of principal components N of the liquefaction products according to obtaining in step B3, the front N column selection in data U is gone out to spectroscopic data H as a setting.
8. the quantitative analysis method of laevulic acid in a kind of biomass liquefying product according to claim 1, it is characterized in that: the switch process of described KS function is: application KS=(ones (sizeab)-Refe) .^2./(2*Refe) is become spectroscopic data the data layout of KS functional form by the Data Format Transform of light intensity, wherein, the reflective light intensity data of Refe for adopting the optical fiber thin-layer chromatogram scanner to gather; Sizeab is the dimension from the data of the reflective light intensity data acquisition that gathers according to the absorbing wavelength of tested component; It is 1 matrix that ones helps the reflective light intensity data-switching of collection according to the absorbing wavelength scope.
9. the quantitative analysis method of laevulic acid in a kind of biomass liquefying product according to claim 1, it is characterized in that: the oblique projection operator described in step B6 is E
s|H=S(S
tp
h ⊥s)
-1s
tp
h ⊥, P
h ⊥=I-P
h=I-H(H
th)
-1h
t, wherein, subscript T represents transpose of a matrix; I is and P
hthe unit matrix that dimension is identical; E
s|Hfor the oblique projection operator; The subspace that the vector that S is measured variable is opened; The adjacent subspace of H for not opening containing the vector of measured variable; P
hfor the projection operator along subspace H to subspace S.
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