CN106323796A - Method for determining content of chemical composition of lignocellulose plant by adopting thermogravimetric analysis meter - Google Patents
Method for determining content of chemical composition of lignocellulose plant by adopting thermogravimetric analysis meter Download PDFInfo
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Abstract
The invention relates to a method for determining content of a chemical composition of a lignocellulose plant by adopting a thermogravimetric analysis meter. The method comprises the following steps: performing programmed temperature rise treatment on a corrected sample set by adopting the thermogravimetric analysis meter, thereby acquiring a thermogravimetric curve of the corrected sample set; determining a target index content of the corrected sample set according to a standard method and taking the target index content as a reference value; combining the thermogravimetric curve of the corrected sample set with the reference value by adopting a partial least squares method to establish a correcting model; substituting the thermogravimetric curve of a to-be-determined sample into the correcting model and calculating, thereby acquiring the target index content of the to-be-determined sample. Compared with the conventional wet chemical analysis, the method provided by the invention has the characteristics of short time, high speed, accurate analysis result, less quantity demand of the sample, and the like. According to the method provided by the invention, the problems of complex steps, long time, high cost and low efficiency of the traditional analysis method can be effectively solved, and the microanalysis and batch-analysis can be performed.
Description
Technical field
The present invention relates to a kind of during lignocellulosic plants chemical composition analysis, modeled by Chemical Measurement
To the mathematical model that phytochemical content is relevant with its thermogravimetric curve, utilize this model that the thermogravimetric curve of testing sample is divided
Analysis, quickly obtains a kind of method of its chemical composition content, and this analysis method demand sample is few, it is quick, accurate to analyze, and belongs to
Lignocellulosic plants analyzes field tests.
Background technology
The chemical composition content of lignocellulosic plants measures, and is Appropriate application plant resources, correct its use valency of assessment
Value and processing method, before being effectively applied to necessity of weaving retting, paper-making pulping, bio-ethanol fermentation pretreatment
Carry.
The commonly used wet-chemical analysis of conventional plant chemical composition content method of testing process, analyze method step numerous and diverse,
Use instrument and medicine is many, analytical cycle length and the drawback such as sample size demand is more, owing to analytical procedure is numerous and diverse, in the process of analysis
The whole process of middle needs big component analysis tester is stood fast at, and is also unfavorable for the raising of work efficiency.Therefore conventional method of analysis is used
When in the face of the analysis of batch samples, its drawback more highlights.Such as at field of textiles, as used country's textile standard
Sample is analyzed by " GB5889-86 Boehmeria chemical composition quantitative analysis method ", need respectively to its moisture content, adipocere matter,
8 compositions such as pectin, hemicellulose, lignin, cellulose, ash and gum content carry out test analysis respectively.And fractions
Test, such as lignin, needs again several little point of experiment test to obtain result.Whole chemical composition analysis of a normal sample
All time is needed to complete.Analyze the bigger situation of sample requirement at some, as in kind of matter research process to cultivation
The evaluation of multiple kind plant and degumming factory the crudefiber crop raw material of many batch separate sources is carried out component analysis, be required to every year
To tens of so that hundreds of sample is analyzed test.Only this item is analyzed, it is necessary to 1-2 position is analyzed tester and carried out the whole year
Work, and owing to its analytical cycle is long, the production the most often affecting factory of analysis result.It addition, to one
The test analysis of sample, needs to consume about 20g raw material and just can obtain all of chemical composition data, and substantial amounts of sample consumes one
Aspect increases analysis cost and analyzes the burden of tester；On the other hand, then a small amount of sample can not be analyzed.
Summary of the invention
It is an object of the invention to provide a kind of modeling by Chemical Measurement and obtain phytochemical content and Qi Re
The mathematical model of weight curve, utilizes the thermogravimetric curve analysis to testing sample of this model, quickly obtains its chemical composition content
A kind of method, its analysis principle is:
Plant mainly contains polysaccharide (pectin, cellulose, hemicellulose) and the big class chemical composition of lignin two, also has simultaneously
There are small part organic solvent extract, water extract and ash.The chemical composition of plant is different due to its classification difference, structure,
Therefore there is different thermal properties.Specifically being reflected in thermogravimetric analysis, the chemical composition of plant can be in different temperature ranges
Producing thermal cracking, thus produce weight change, generate thermogravimetric curve, sample chemical component content changes, the thermogravimetric curve of generation
The most different；
Therefore, thermogravimetric curve, outside reflection raw material Thermal Information, also carries the information of a large amount of chemical composition content.
Chemical Measurement is i.e. built between measured value and the state of system to chemical system by the means such as statistics and mathematical modeling
The subject of vertical contact.
According to above-mentioned principle, by the present invention in that and use Chemical Measurement means, by the chemical composition content of Calibration
Being associated with thermogravimetric curve, modeling obtains forecast model, and is predicted unknown sample with this model.
The present invention adopts the following technical scheme that a kind of utilization Thermogravimetric analysis quickly measures lignocellulosic plants chemistry
The method of component content, it is characterised in that comprise the following steps:
The first step, sample thermogravimetric analysis step:
(1), take respectively more than 60 different sources, different growing stages plant variety as testing sample；To collect
Testing sample be divided into two groups: one group as Calibration, another group is as verification sample collection；Wherein, Calibration
Sample size is 41 with the quantity ratio of the sample of verification sample collection；
(2), respectively each sample of each sample of above-mentioned Calibration Yu verification sample collection is dried at 105 DEG C 4h with
Up to over dry；Then, by sample comminution, cross 40 mesh sieves, obtain the powder of each sample；
Weigh the powder 20mg of each sample respectively, put into and thermogravimetric analyzer carries out thermogravimetric analysis, from room temperature 20 DEG C beginning,
Carry out being warming up to 900 DEG C with 5 DEG C/min, stop heating up, and use liquid nitrogen cooling, obtain the sample of all Calibrations one by one
The respective powder thermal gravimetric analysis curve with the sample of verification sample collection；
Second step, sample wet-chemical analysis step:
To the sample of all Calibrations with the sample of verification sample collection respective lignin, holocellulose survey
Fixed；And the hemicellulose of the sample after having measured holocellulose is measured, obtain the lignin of sample, hemicellulose and fibre
Dimension cellulose content reference value；
3rd step, thermogravimetric curve combines samples Reference value and sets up the step of model:
The Calibration thermogravimetric curve that will collect, uses thermogravimetric analysis software to carry out baseline deduction, first derivative pre-
Process, draw the pretreatment thermogravimetric curve comprising the characteristic information that correcting sample concentrates sample chemical component content；
Then, the pretreatment measured lignin, hemicellulose and content of cellulose data concentrated with correcting sample
Thermogravimetric curve data combine, and use partial least square method to set up calibration model；
4th step, modelling verification step:
The verification sample collection original thermogravimetric curve data that will obtain, after carrying out the above-mentioned 3rd identical pretreatment of step, will locate in advance
In reason thermogravimetric curve data input calibration model, draw verification sample collection predictive value, and measure with utilizing wet chemical analytical method
Verification sample concentrates phytochemical content comparison, verifies calibration model, it is determined that whether verification sample integrates as correction
Out-of-bounds point outside scope.
As verification sample collection does not contains out-of-bounds point, illustrate that model is the most perfect, be not required to optimize；As containing out-of-bounds point, add
Out-of-bounds put and again re-establish calibration model by calibration model establishment step, the most perfect to calibration model, optimize and check school
The performance of positive model, each modeling parameters of loop optimization, finally determine optimal parameter so that modelling verification collection sample predictive value with
Chemical analysis value is consistent, obtains optimal models；
5th step, sample prediction steps:
Plant sample to be measured is pulverized, obtains thermogravimetric curve data through thermogravimetric analysis, the condition of analysis and method and acquisition
Condition and the method for the thermogravimetric curve of Calibration are consistent, after thermogravimetric curve data are carried out pretreatment, are updated to correction
In model, i.e. obtain the chemical composition content value of this sample, wherein, thermogravimetric curve preprocess method and the thermogravimetric of Calibration
Curve pretreatment is consistent.
Being preferably, above-mentioned lignocellulosic plants is timber, fibre of flax for textile material or straw.
Further preferably, the above-mentioned Thermogravimetric analysis that uses quickly measures lignocellulosic plants chemical composition content
Method, uses the analysis method of regenerative resource National Laboratory of the U.S. to be measured the lignin of sample；
Employing country papermaking standard: the mensuration of GB 02677.10-1995-T paper making raw material holocellulose content, to sample
Holocellulose be measured；
To having measured the sample after holocellulose, use country's textile standard: GB5889-86 Boehmeria chemical composition is quantitatively divided
Analysis method, is measured the hemicellulose of sample, obtains sample chemical component content reference value.
The direct technology effect that technique scheme is brought is: sample requirement few (20mg), analysis time are short, and (3h can survey
Sample lignin, hemicellulose and content of cellulose data), manpower demand low (only experiment start and at the end of need people
Work operates, and 100 samples need the artificial directly operating time less than 8h)；And whole test process is not required to any chemical cost,
Testing expense is low, safety is high, simple to operate, analysis process is short in analysis, without follow-up sample residue and chemical waste fluid process.
In order to be better understood from above-mentioned technique effect, labor be described as follows:
In technique scheme, choose and can ensure that no less than 60 different sources, the plant variety of different growing stages
The robustness of final cast and universality；The characteristic information of corresponding plant chemical ingredient is carried by the model set up less than 60 sample sizes
Taking not, final model is sane not, is easily generated out-of-bounds point, also easily causes bigger forecast error；And the region of sample and
The kinds such as trophophase are the most single, also the pre-test sample of different geographical, different growing stages can not be carried out Accurate Prediction.
In follow-up thermogravimetric analysis step, use the heating rate of 5 DEG C/min can to obtain with the shortest analysis time
The plant thermogravimetric curve that quality is the highest, reduces programming rate and then can make overall thermal weight analysis overlong time, and increase heating rate,
The temperature hysteresis recorded is the most serious, and initial weightless temperature and final temperature measured value become the highest, decomposition temperature
Scope also can become wider, and for decomposing weightless less sensitive chemical composition, if heating rate is too fast, it has little time to make
Going out to sufficiently respond to, weightless step will indeterminacy or do not measure.
Wherein, the chemical analysis method of employing is one of key point of the present invention, has non-the normally off to the quality of final mask
The effect of key.
This is because, existing plant chemical ingredient analyzes method at different industries and different field even country variant all
There is different systems.Partial analysis system due to formulate the time early, the reason such as subject range is narrow, to conventional plant variety
Study point analysis meeting and produce bigger analytical error；Inaccurate chemical composition reference value then directly affects the steady of final mask
Qualitative and accuracy.
The analysis method that the present invention uses is in recent years by recognized by a large amount of scholars and commonly used, can generally be suitable for
In the analysis method of multi items plant lignin, hemicellulose and cellulose, the method both ensure that precision of analysis,
There is again analysis universality.
Wherein, used thermogravimetric curve combines with plant chemical ingredient data, uses Chemical Measurement means to close
Joint construction mould, is the key problem in technology point of the present invention, is also the present invention " inventive point " place.
For correct understanding this point, explanation in detail below and explanation:
Known in those skilled in the art, thermogravimetric analysis is that the multicomponent mixture chemical composition content of a kind of routine is quantitative
Analysis method.Its principle is that (oxygen, air or nitrogen) carries out programmed heating to mixture, due to mixture under certain environment
Each chemical composition thermal property there are differences, its corresponding substance decomposition or vaporization under different temperature ranges, so that
The absolute mass of mixture produces change, and on this reacting condition to thermogravimetric curve, thermogravimetric analysis is then according to thermogravimetric curve
Change, and then calculate the absolute mass of corresponding chemical substance under relevant temperature, compared with the initial mass of mixture, then obtain
This compound content in the mixture.
But, the chemical composition that lignocellulosic plants contains is extremely complex, usually contains cellulose, hemicellulose, wood
Quality three major types composition.It is to say, lignocellulosic plants is different from other organic material.
These chemical compositions (in addition to cellulose) of lignocellulosic plants are a class chemistry similar mixture of substances
Being referred to as, hemicellulose is the heteromultimer being made up of several different types of monosaccharide, and lignin is that one is widely present in and plants
Armaticity high polymer containing oxo phenylpropanol or derivatives thereof construction unit in unbodied, molecular structure in object, fine
The macromolecular polysaccharide that dimension element is made up of glucose, these chemical compositions also have the different degree of polymerization in same plant；
And these chemical compositions of difference plant also there are differences in structure and particular make-up；The character body of above-mentioned plant chemical ingredient
In thermogravimetric analysis now, direct impact is exactly that the thermal degradation of each chemical composition all exists certain temperature range, and different
There is coincidence in the degradation temperature interval of chemical composition, thus causes the difficulty of conventional thermogravimetric analysis direct quantitative；
Further, since kind is different, source different, growth conditions is different, the heat of the same chemical composition of different samples is divided
Solving temperature range, degradation speed is the most different, further increases the difficulty of thermogravimetric analysis direct quantitative.
Therefore, conventional thermogravimetric analysis can not carry out the direct quantitative of chemical composition to lignocellulosic plants.In view of upper
State reason, the analysis method of lignocellulosic plants chemical composition is still commonly used wet-chemical analysis method.It is well known that
Conventional method of analysis exists that step is numerous and diverse, use instrument and medicine is many, analytical cycle length and the drawback such as sample size demand is more.
The present invention then solves, from another angle, the problem that above-mentioned thermogravimetric analysis exists.As it has been described above, lignocellulose
The thermogravimetric curve of plant is the synthesis result of one or more chemical compositions degraded in uniform temperature interval, therefore can not be the most right
It resolves, and then carries out quantitative analysis.
But from another angle, the thermogravimetric curve data of this temperature range contain the part of one or more chemical compositions
Information, therefore the thermal degradation information of any chemical composition is then the comprehensive anti-of the information of several temperature ranges on thermogravimetric curve
Reflect.
Therefore, in theory, the content information of a certain chemical composition of sample, then can be by the several interval of thermogravimetric curve
Information carrys out concentrated expression, and the content of the most a certain chemical composition exists certain number with the data of several temperature ranges on thermogravimetric curve
Relation, this relation then can be extracted by Chemical Measurement means, associate, and by substantial amounts of Calibration data
Progressively correct, optimize, finally set up the correlation model of this chemical composition content and thermogravimetric curve.
The technological means that technique scheme combines by using statistics and Chemical Measurement means, has reached to use
Thermogravimetric analysis carrys out the target of quantitative plant chemical ingredient.Overcome owing to kind is different, source is different, growth conditions is different, institute
The data parsing difficulty that the same chemical composition thermogravimetric curve necessarily caused offsets, different chemical composition thermogravimetric curve overlap is brought
A difficult problem for this prior art.
What is more important, technique scheme is using the modeling to plant chemical ingredient of the above-mentioned Chemical Measurement means
During, typically that the standard content data of Calibration are relevant to two in thermogravimetric curve data or several main gene
Connection, the content data of a kind of chemical composition can several characteristics of corresponding thermogravimetric curve, these characteristics are correction samples
Product concentrate the common trait information of this chemical composition of all samples, and this mode considerably increases the stability of model, it is to avoid
During modeling and prediction different due to product, the fine difference that region difference is brought, improve the prediction energy of model
Power and precision.
It should be added that, similar with the present invention also has near infrared spectroscopy, but both have obvious difference.Tool
Body is described as follows:
Although near infrared spectroscopy and the present invention are consistent in subprogram, but they have significantly different: at analysis principle
On, near infrared spectroscopy is that the hydrogen bond information in plant and chemical composition are combined modeling.
And the present invention is to use plant chemical ingredient to have the principle of thermal degradation performance difference to be modeled；At near-infrared
In spectrographic method, although hydrogen bond information can be likewise covered by the content information of plant chemical ingredient, but the information that hydrogen bond comprises is too much, removes
Outside above-mentioned information, also comprising other chemistry, physics even partial structural information of plant, this results near infrared spectroscopy to spy
The feature information extraction difficulty of given data, not only modeling work amount is big, if can not accurately extract and chemical composition content
Corresponding spectral information, robustness and the accuracy of its final mask are the highest；
Thermal gravimetric analysis curve the most only have expressed plant chemical ingredient thermal degradation information, therefore feature information extraction letter
Single, become more readily available the forecast model of optimum；
On preparation of samples, near infrared spectroscopy needs the sample of more than 5g just can carry out spectra collection, and the present invention uses
Thermogravimetry, general 20mg sample can be analyzed, and therefore sample requirements is few, and the sample analysis of trace is had uniqueness
Advantage；In experimental implementation, near infrared spectroscopy needs manually successively sample to be carried out spectral scan, does not possess automatization；
And the thermogravimetric analysis rule that the present invention uses is equipped with batch sample automatic analysis system, is setting test parameters
After, can automatically a large amount of samples be analyzed.Thus, save human cost.
In sum, compared with prior art, thermogravimetric analyzer used in the present invention measures lignocellulosic plants
The method learning component content, analyzes the content of plant chemical ingredient by obtaining the thermogravimetric curve of plant, and it has following skill
Art effect:
(1) sample size demand is few, is suitable for micro-example analysis, and common wet chemical method to obtain whole chemical composition content
Then need the sample of more than 10g, and the thermogravimetric analysis of the application uses sample to be only about 20mg；
(2) test is quickly, and much common wet chemical method then needs 3 days more just can obtain whole chemical composition content,
And one sample of thermogravimetric analysis of the present invention is time-consumingly only about 3h；
(3) recruitment of the present invention is few, work efficiency is high and can carry out batch quantity analysis, and wet-chemical analysis can only be successively to sample
It is analyzed, owing to analytical procedure is numerous and diverse, operates various, and need staff's whole process to guard, and the thermogravimetric analysis of the present invention
Instrument is equipped with automatic sample handling system, and thermogravimetric analysis can be surveyed automatically without attention of staff after early stage is provided with
Examination is analyzed.
(4) without any chemical reagent consumption, common wet-chemical analysis needs the consumption of a large amount of chemical reagent to obtain data,
Thermogravimetric analysis of the present invention is not required to any chemical reagent consumption and i.e. can get desired data.
Accompanying drawing explanation
Fig. 1 is the flow chart of the present invention；
Fig. 2 is the testing result comparison diagram with chemical analysis that predicts the outcome of the content of lignin of embodiment 1；
Fig. 3 is the testing result comparison diagram with chemical analysis that predicts the outcome of the content of cellulose of embodiment 1；
Fig. 4 is the testing result comparison diagram with chemical analysis that predicts the outcome of the hemicellulose level of embodiment 1.
Detailed description of the invention
Below in conjunction with the accompanying drawings and embodiment, the present invention is described in detail.
Embodiment 1
As a example by wood raw material
Choose wood raw material 60 parts, wherein: 25 parts derive from Linyi, Shandong, and Kweiyang, Guizhou, 15 parts of sources, 20 parts derive from
Changsha；Being respectively prepared sample, every part of example weight is 50g.
All samples, 105 DEG C of crushed after being dried, is crossed 40 mesh sieves, is obtained sample powder, each sample about 30g, be then divided into
Two parts, a (20mg) carries out thermogravimetric analysis, and another part (30g) carries out wet-chemical analysis；
As it is shown in figure 1, Calibration and testing sample thermogravimetric curve gather: weigh sample about 20mg, put into thermogravimetric and divide
Analyzer carries out thermogravimetric analysis, and gathers thermogravimetric curve, heating schedule be provided that sample from the beginning of room temperature 20 DEG C, with 5 DEG C/
Min heats up, and temperature is increased to 900 DEG C and stops heating up, and uses liquid nitrogen cooling, and analysis terminates；
The mensuration of Calibration reference value: with reference to the analysis method of regenerative resource National Laboratory of the U.S.
" Determination of Structural Carbohydrates and Lignin in Biomass " wooden to sample
Element is measured, with reference to country's papermaking standard " mensuration of GB 02677.10-1995-T paper making raw material holocellulose content " to sample
The holocellulose of product is measured, to having measured the sample after holocellulose, with reference to country textile standard " GB5889-86 Boehmeria
Chemical composition quantitative analysis method " hemicellulose of sample is measured；
The foundation of calibration model: choose 48 samples and set up calibration model, the Calibration thermogravimetric curve that will collect
Use thermogravimetric analysis software to carry out baseline deduction, first derivative pretreatment, show that correcting sample concentrates sample chemical component content
Characteristic information, the characteristic information that the content data recorded is concentrated with correcting sample is combined, use partial least square method build
Vertical calibration model；
The checking of calibration model: use other 12 samples that the calibration model set up is verified, the checking that will obtain
Sample sets original thermogravimetric curve data, after carrying out pretreatment, in input calibration model, draw verification sample collection predictive value, and with
The verification sample utilizing wet chemical analytical method to measure concentrates phytochemical content comparison, verifies calibration model.
The result is as follows:
Table 1: verification sample collection wood chemical compositions test chemical value contrasts knot with the predictive value of the method gained of the present invention
Really
Table 2 chemical analysis and the method comparing result of the present invention
| Method | Analytical error | Sample size | The single sample used time | Total used time | Sample consumes | Continuous batch is tested |
| Chemical analysis | ≤ 0.5% | 12 | 3d | 36d | 20g | No |
| The present invention | < 0.4% | 12 | 3h | 1.5d | 20mg | Can |
From the data of upper table 1 and Fig. 2-Fig. 4 it can be seen that the method for the use present invention can be to the lignin of timber, fiber
Element and hemicellulose are predicted accurately, it was predicted that result and test value coefficient of determination R2Value is above 0.95, i.e. coefficient R
Value is above 0.97；
Predictive value is respectively less than 0.4% with the mean square deviation of test value, it was predicted that error is less, it was demonstrated that the method for the present invention can be to sample
Product carry out the accurate test of chemical composition.
Table 2 shows, on the basis of being successfully established forecast model, follow-up unknown sample is tested by the method for the present invention, makes
Being only 20mg by sample size, the time of test lignin, hemicellulose and cellulose is 3h；Conventional method needs the sample size to be
20g, the time of test adipocere matter, lignin, hemicellulose and cellulose is 3 days.
Therefore, present invention substantially reduces sample size and the testing time of test.
It addition, thermogravimetric analyzer has batch quantity analysis test function, can be continuously to 50 samples in the case of unmanned
Product are tested, and further save analysis testing time and manpower consumption.
Embodiment 2
As a example by Kenaf plant, choosing kenaf raw material 80 parts, wherein, the place of production is 40 parts of Hunan, the place of production is the 20 of Shandong
Part, the place of production are 20 parts of Xinjiang；Being respectively prepared sample, every part of example weight is 50g.
All samples, 105 DEG C of crushed after being dried, is crossed 40 mesh sieves, is obtained sample powder, each sample about 30g, be then divided into
Two parts, a (20mg) carries out thermogravimetric analysis, and another part (30g) carries out wet-chemical analysis；
As it is shown in figure 1, Calibration and testing sample thermogravimetric curve gather: weigh sample about 20mg, put into thermogravimetric and divide
Analyzer carries out thermogravimetric analysis, and gathers thermogravimetric curve, heating schedule be provided that sample from the beginning of room temperature 20 DEG C, with 5 DEG C/
Min heats up, and temperature is increased to 900 DEG C and stops heating up, and uses liquid nitrogen cooling, and analysis terminates；
The mensuration of Calibration reference value: with reference to the analysis method of regenerative resource National Laboratory of the U.S.
" Determination of Structural Carbohydrates and Lignin in Biomass " wooden to sample
Element is measured, with reference to country's papermaking standard " mensuration of GB 02677.10-1995-T paper making raw material holocellulose content " to sample
The holocellulose of product is measured, to having measured the sample after holocellulose, with reference to country textile standard " GB5889-86 Boehmeria
Chemical composition quantitative analysis method " hemicellulose of sample is measured；
The foundation of calibration model: choose 60 samples and set up calibration model, the Calibration thermogravimetric curve that will collect
Use thermogravimetric analysis software to carry out baseline deduction, first derivative pretreatment, show that correcting sample concentrates sample chemical component content
Characteristic information, the characteristic information that the content data recorded is concentrated with correcting sample is combined, use partial least square method build
Vertical calibration model；
The checking of calibration model: use other 20 samples that the calibration model set up is verified, the checking that will obtain
Sample sets original thermogravimetric curve data, after carrying out pretreatment, in input calibration model, draw verification sample collection predictive value, and with
The verification sample utilizing wet chemical analytical method to measure concentrates phytochemical content comparison, verifies calibration model.
Result shows, uses the method for the present invention to tie the prediction of lignin, cellulose and the hemicellulose of kenaf wood
Fruit is respectively as follows: 0.98,0.97,0.93 with test chemical value correlation coefficient；Prediction mean square deviation is respectively as follows: 0.21%, and 0.37%,
0.29%.
Embodiment 3
As a example by corn plant, choose corn stalk raw material 120 parts, wherein, the place of production be highly dense 40 parts, Shandong, the place of production be mountain
40 parts of Liaocheng of east, the place of production are 40 parts of Dezhou, Shandong；Being respectively prepared sample, every part of example weight is 50g.
All samples, 105 DEG C of crushed after being dried, is crossed 40 mesh sieves, is obtained sample powder, each sample about 30g, be then divided into
Two parts, a (20mg) carries out thermogravimetric analysis, and another part (30g) carries out wet-chemical analysis；
As it is shown in figure 1, Calibration and testing sample thermogravimetric curve gather: weigh sample about 20mg, put into thermogravimetric and divide
Analyzer carries out thermogravimetric analysis, and gathers thermogravimetric curve, heating schedule be provided that sample from the beginning of room temperature 20 DEG C, with 5 DEG C/
Min heats up, and temperature is increased to 900 DEG C and stops heating up, and uses liquid nitrogen cooling, and analysis terminates；
The mensuration of Calibration reference value: with reference to the analysis method of regenerative resource National Laboratory of the U.S.
" Determination of Structural Carbohydrates and Lignin in Biomass " wooden to sample
Element is measured, with reference to country's papermaking standard " mensuration of GB 02677.10-1995-T paper making raw material holocellulose content " to sample
The holocellulose of product is measured, to having measured the sample after holocellulose, with reference to country textile standard " GB5889-86 Boehmeria
Chemical composition quantitative analysis method " hemicellulose of sample is measured；
The foundation of calibration model: choose 90 samples and set up calibration model, the Calibration thermogravimetric curve that will collect
Use thermogravimetric analysis software to carry out baseline deduction, first derivative pretreatment, show that correcting sample concentrates sample chemical component content
Characteristic information, the characteristic information that the content data recorded is concentrated with correcting sample is combined, use partial least square method build
Vertical calibration model；
The checking of calibration model: use other 30 samples that the calibration model set up is verified, the checking that will obtain
Sample sets original thermogravimetric curve data, after carrying out pretreatment, in input calibration model, draw verification sample collection predictive value, and with
The verification sample utilizing wet chemical analytical method to measure concentrates phytochemical content comparison, verifies calibration model.
Result shows, uses the method for the present invention to tie the prediction of lignin, cellulose and the hemicellulose of kenaf wood
Fruit is respectively as follows: 0.94,0.99,0.97 with test chemical value correlation coefficient；Prediction mean square deviation is respectively as follows: 0.13%, and 0.34%,
0.32%.
Claims (3)
1. using the method that Thermogravimetric analysis quickly measures lignocellulosic plants chemical composition content, its feature exists
In, comprise the following steps:
The first step, sample thermogravimetric analysis step:
(1), take respectively more than 60 different sources, different growing stages plant variety as testing sample；By treating of collecting
Test sample product be divided into two groups: one group as Calibration, another group is as verification sample collection；Wherein, the sample of Calibration
Quantity is 41 with the quantity ratio of the sample of verification sample collection；
(2), respectively each sample of each sample of above-mentioned Calibration Yu verification sample collection is dried 4h with up at 105 DEG C
Over dry；Then, by sample comminution, cross 40 mesh sieves, obtain the powder of each sample；
Weigh the powder 20mg of each sample respectively, put into and thermogravimetric analyzer carries out thermogravimetric analysis, from room temperature 20 DEG C beginning, with 5
DEG C/min carries out being warming up to 900 DEG C, stops heating up, and uses liquid nitrogen cooling, obtain one by one the sample of all Calibrations with
The sample respective powder thermal gravimetric analysis curve of verification sample collection；
Second step, sample wet-chemical analysis step:
To the sample of all Calibrations, respective lignin, holocellulose are measured with the sample of verification sample collection；And
The hemicellulose of the sample after having measured holocellulose is measured, obtains the lignin of sample, hemicellulose and cellulose
Content reference value；
3rd step, thermogravimetric curve combines samples Reference value and sets up the step of model:
The Calibration thermogravimetric curve that will collect, uses thermogravimetric analysis software to carry out baseline deduction, first derivative pretreatment,
Draw the pretreatment thermogravimetric curve comprising the characteristic information that correcting sample concentrates sample chemical component content；
Then, the pretreatment thermogravimetric measured lignin, hemicellulose and content of cellulose data concentrated with correcting sample
Curve data combines, and uses partial least square method to set up calibration model；
4th step, modelling verification step:
The verification sample collection original thermogravimetric curve data that will obtain, after carrying out the above-mentioned 3rd identical pretreatment of step, by pretreatment heat
In weight curve data input calibration model, draw verification sample collection predictive value, and with the checking utilizing wet chemical analytical method to measure
In sample sets, phytochemical content comparison, verifies calibration model, it is determined that whether verification sample integrates as correcting range
Outside out-of-bounds point.
As verification sample collection does not contains out-of-bounds point, illustrate that model is the most perfect, be not required to optimize；As containing out-of-bounds point, add out-of-bounds
Point re-establishes calibration model by calibration model establishment step again, the most perfect to calibration model, optimizes and checks straightening die
The performance of type, each modeling parameters of loop optimization, finally determine optimal parameter so that modelling verification collection sample predictive value and chemistry
Assay value is consistent, obtains optimal models；
5th step, sample prediction steps:
Being pulverized by plant sample to be measured, obtain thermogravimetric curve data through thermogravimetric analysis, the condition of analysis and method correct with acquisition
Condition and the method for the thermogravimetric curve of sample sets are consistent, after thermogravimetric curve data are carried out pretreatment, are updated to calibration model
In, i.e. obtain the chemical composition content value of this sample, wherein, thermogravimetric curve preprocess method and the thermogravimetric curve of Calibration
Pretreatment is consistent.
Utilization Thermogravimetric analysis the most according to claim 1 quickly measures lignocellulosic plants chemical composition content
Method, it is characterised in that described lignocellulosic plants is timber, fibre of flax for textile material or straw.
Utilization Thermogravimetric analysis the most according to claim 1 and 2 quickly measures lignocellulosic plants chemical composition and contains
The method of amount, it is characterised in that use the analysis method of regenerative resource National Laboratory of the U.S. that the lignin of sample is carried out
Measure；
Employing country papermaking standard: the mensuration of GB 02677.10-1995-T paper making raw material holocellulose content, combines sample
Cellulose is measured；
To having measured the sample after holocellulose, use country's textile standard: GB5889-86 Boehmeria chemical composition quantitative analysis side
Method, is measured the hemicellulose of sample, obtains sample chemical component content reference value.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109030550A (en) * | 2018-06-04 | 2018-12-18 | 安徽天宇磁业股份有限公司 | A kind of Nd-Fe-B permanent magnet material coating determination method |
| ES2730430A1 (en) * | 2018-05-08 | 2019-11-11 | Univ Huelva | METHOD FOR THE DETERMINATION OF THE CONTENT OF HEMICELLULOSE, CELLULOSE AND LIGNIN IN BIOMASS AND LIGNOCELLULOSTIC PASTES (Machine-translation by Google Translate, not legally binding) |
| CN112798459A (en) * | 2020-12-31 | 2021-05-14 | 宁波诺丁汉新材料研究院有限公司 | Full-automatic lignocellulose determinator and determination method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1888860A (en) * | 2006-07-24 | 2007-01-03 | 中国林业科学研究院木材工业研究所 | Establishment of chemical composition content model in plant fiber material and content determining method |
| CN102539566A (en) * | 2011-12-28 | 2012-07-04 | 河南中医学院 | Method for fast detecting content of dioscin in dioscorea zingiberensis by utilizing near infrared spectrum technology |
| WO2014078474A1 (en) * | 2012-11-15 | 2014-05-22 | Vertichem Corporation | Method for evaluation of lignin |
| CN103852441A (en) * | 2014-02-21 | 2014-06-11 | 广东中烟工业有限责任公司 | Method for quantitative detection of tobacco lignin by adopting mid-infrared spectroscopy |
| CN105203579A (en) * | 2015-09-14 | 2015-12-30 | 中国环境科学研究院 | Thermal analysis determination method for plant biomass lignin content |
-
2016
- 2016-10-27 CN CN201610957153.4A patent/CN106323796B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1888860A (en) * | 2006-07-24 | 2007-01-03 | 中国林业科学研究院木材工业研究所 | Establishment of chemical composition content model in plant fiber material and content determining method |
| CN102539566A (en) * | 2011-12-28 | 2012-07-04 | 河南中医学院 | Method for fast detecting content of dioscin in dioscorea zingiberensis by utilizing near infrared spectrum technology |
| WO2014078474A1 (en) * | 2012-11-15 | 2014-05-22 | Vertichem Corporation | Method for evaluation of lignin |
| CN103852441A (en) * | 2014-02-21 | 2014-06-11 | 广东中烟工业有限责任公司 | Method for quantitative detection of tobacco lignin by adopting mid-infrared spectroscopy |
| CN105203579A (en) * | 2015-09-14 | 2015-12-30 | 中国环境科学研究院 | Thermal analysis determination method for plant biomass lignin content |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2730430A1 (en) * | 2018-05-08 | 2019-11-11 | Univ Huelva | METHOD FOR THE DETERMINATION OF THE CONTENT OF HEMICELLULOSE, CELLULOSE AND LIGNIN IN BIOMASS AND LIGNOCELLULOSTIC PASTES (Machine-translation by Google Translate, not legally binding) |
| CN109030550A (en) * | 2018-06-04 | 2018-12-18 | 安徽天宇磁业股份有限公司 | A kind of Nd-Fe-B permanent magnet material coating determination method |
| CN112798459A (en) * | 2020-12-31 | 2021-05-14 | 宁波诺丁汉新材料研究院有限公司 | Full-automatic lignocellulose determinator and determination method |
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