CN104297272B - A kind of CT characterizing method of coal directly-liquefied residue sample - Google Patents

Abstract

The present invention relates to the visualization characterization technique of coal directly-liquefied residue sample organic component distribution, the CT characterizing method of a kind of coal directly-liquefied residue sample.The CT characterizing method of a kind of coal directly-liquefied residue sample, comprises the steps: the first step, the sampling of coal directly-liquefied residue sample and pretest；Second step, the X-ray absorption specificity analysis of the second coal directly-liquefied residue sample each ash composition；3rd step, the second coal directly-liquefied residue sample component packet；4th step, the CT experiment of the second coal directly-liquefied residue sample；5th step, setting up physical model, in cutting into slices CT, different component makes a distinction discriminating；6th step, rejecting inorganic component, further discriminate between organic component, utilizes different colours to show the distribution of different organic component in a model, it is achieved the visualization of coal directly-liquefied residue sample organic component distribution form characterizes.Physical model of the present invention can be greatly improved computational efficiency, can be used for the sign of a large amount of sample.

Description

A kind of CT characterizing method of coal directly-liquefied residue sample

Technical field

The visualization that the present invention relates to the distribution of coal directly-liquefied residue sample organic component characterizes skill Art, the CT characterizing method of a kind of coal directly-liquefied residue sample.

Background technology

Coal directly-liquefied residue is the product after coal liquefaction, its composition can be divided into organic component and The big class of inorganic component two.Wherein organic component comprises bitumen, heavy oil and unconverted coal Substrate；Inorganic component comprises the catalyst added in the mineral in raw coal and liquefaction process.Coal Organic component in direct liquefaction residue sample has higher caloric value and value, to coal The distribution form of direct liquefaction residue sample organic component and combination carry out visualization and characterize Contribute to developing the recovery method of utility in new residue.

The visualization characterization technique of coal directly-liquefied residue sample specifically includes that scanning electron microscope at present Method, optical microscopy etc..Scanning electron microscope Momentum profiles can be in sample area interested Elemental redistribution carry out visualization differentiate, optical microscope can observe sample not the most easily Pattern with component.But either scanning electron microscope or optical microscope, is all difficult to observe coal The distribution form of different organic components and the mode that be combined with each other in direct liquefaction residue sample.

X ray CT imaging is a kind of important material morphology, structures visualization characterization technique.Especially It it is the appearance of Microfocus X-ray CT and the Synchrotron Radiation Computed Tomography technology quantitive CT table that can realize multiple material Levy.But in the CT of coal directly-liquefied residue sample characterizes, there is many difficulties.In residue Different organic components have close X-ray absorption coefficient, and existing carrying out image threshold segmentation method is Depend directly on the X-ray absorption coefficient value of sample different component, due to experimental error and part The existence of bulk effect, is difficult to make a distinction organic components different in residue.It addition, it is residual The concrete molecular formula of slag Minerals is difficult to determine, and has a large amount of ore deposit less than CT resolution Thing component exists, and these factors can cause the X-ray absorption that in CT section, pixel is showed Coefficient is difficult to set up directly associating with residue component, adds what organic component in residue was distinguished Difficulty.

Summary of the invention

The present invention solves that the visualization characterization technique of existing coal directly-liquefied residue sample exists The technical problem that is difficult to differentiate between of organic component, it is provided that a kind of coal directly-liquefied residue sample CT characterizing method.

The present invention is achieved by the following technical solutions: a kind of coal directly-liquefied residue sample CT characterizing method, comprises the steps: the first step, the sampling of coal directly-liquefied residue sample And pretest: choose for organic component molecule in a collection of coal directly-liquefied residue sample First coal directly-liquefied residue sample of formula, mineral grey composition test, and test for CT The second coal directly-liquefied residue sample；The first coal directly-liquefied residue is obtained by laboratory facilities Sample fundamental property test data, described coal directly-liquefied residue sample fundamental property test data Including content of ashes, ash composition and ash component content, coal in coal directly-liquefied residue sample Unconverted matrix of coal, heavy oil and bitumen molecular formula in direct liquefaction residue sample；According to Coal directly-liquefied residue sample ash component content infers that each ash composition is in total ash Volume fraction；Second step, the X-ray of the second coal directly-liquefied residue sample each ash composition Absorption characteristic is analyzed: calculate the second direct liquid of coal under different x-ray energy according to formula (1) Change the ratio of the X-ray absorption amount of each ash composition in residue sample,

$y_1=\frac{{\mathrm{\μ}}_i\left(x\right)\×V_i}{{\mathrm{\μ}}_m\left(x\right)\×V_m}---\left(1\right)$

In formula (1), i represents different ash compositions；M represents with reference to ash composition, described reference Ash composition is composition most to X-ray absorption in ash；X represents X-ray energy； μ_i(x) and μ_mX () represents ash component i respectively and is x keV with reference to ash composition at energy X-ray linear absorption coefficient；V_iAnd V_mRepresent ash component i respectively and be divided into reference to ash The volume fraction divided；Neglect the ratio ash composition less than or equal to CT experimental noise level, Remainder ash composition；Described remainder ash composition is with reference to ash composition by one With remaining ash composition composition；3rd step, the second coal directly-liquefied residue sample component packet: Remainder ash composition and unconverted coal under different x-ray energy is calculated according to formula (2) The ratio of the X-ray linear absorption coefficient of substrate,

$y_2=\frac{{\mathrm{\μ}}_{\mathrm{\α}}^r\left(x\right)}{{\mathrm{\μ}}_0^r\left(x\right)}---\left(2\right)$

α in formula (2) represents different remainder ash compositions,Represent residue Part of ash composition α is at the X-ray linear absorption coefficient that energy is x keV；Represent In residue, unconverted matrix of coal is at the X-ray linear absorption coefficient that energy is x keV；Make Each remainder ash composition and the X-ray line of unconverted matrix of coal under different x-ray energy Property absorptance ratio curve, is grouped remainder ash composition, and X-ray is linearly inhaled The ash that receipts coefficient curve is parallel to each other becomes to be divided into a group；4th step, the second direct liquid of coal Change the CT experiment of residue sample: find out the X-ray linear absorption coefficient between different group bent Line the most uneven energy section, chooses three X-ray experiment energy in above-mentioned energy section Amount carries out CT experiment respectively, it is thus achieved that multiple projection images, and the imaging of CT experimental projection picture is differentiated Rate is a；Above-mentioned projection image is carried out CT section reconstruct, restructuring procedure is deducted in projection image Bright background and dark background, the size of the distinguishable unit of minimum of CT section is a × a, The CT section of three energy is chosen three CT sections of counter sample same position, at this Picture quality is chosen preferably and under hole and the less region of mineral carry out in three CT section One step calculates, the area pixel cut out a size of c × d；

5th step, setting up physical model, in cutting into slices CT, different component makes a distinction discriminating: model Being made up of N (N=e × f) individual simple cubic lattice, each simple cubic lattice is selected with in CT section The pixel one_to_one corresponding in region, the size of each simple cubic lattice is a × a × a, to all The linear optimal planning that simple cubic lattice is carried out as shown in (3) formula calculates:

$\left\{\begin{array}{c}\underset{c=1}{\overset{C}{\Σ}}{\mathrm{\μ}}^{(1,c)}{V}_n^{\left(c\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(1\right)}\\ \underset{c=1}{\overset{C}{\Σ}}{\mathrm{\μ}}^{(2,c)}{V}_n^{\left(c\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(2\right)}\\ \underset{c=1}{\overset{C}{\Σ}}{\mathrm{\μ}}^{(3,c)}{V}_n^{\left(c\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(3\right)}\\ \underset{c=0}{\overset{C}{\Σ}}{V}_n^{\left(c\right)}=1\\ 0\≤V_n^{\left(c\right)}\≤1\end{array}\right.---\left(3\right)$

Wherein c (=0,1,2 ... .C) different value respectively corresponding different packet, c=0 pair Answer hole group；C=1 correspondence Organic substance group, c=2,3 ... C correspondence remainder ash is divided into Ash component group；Represent the volume fraction being grouped c in the n-th simple cubic lattice；μ^(1,c)、 μ^(2,c)、μ^(3,c)Represent packet c X-ray linear absorption under three CT test energy respectively Coefficient, during c=1, μ^(1,c)、μ^(2,c)、μ^(3,c)Equal to the matrix of coal in Organic substance, heavy oil, Bitumen is the meansigma methods of absorptance under corresponding X-ray energy, c=2, and 3 ... during C, μ^(1,c)、μ^(2,c)、μ^(3,c)Linearly inhale equal to each component X-ray under corresponding energy in packet c Receive coefficient and be multiplied by this component volume fraction in a packet, add up summation and obtain total value, then divided by The volume fraction that packet c is total；Represent that the n-th letter that experiment obtains is vertical respectively Cage X-ray linear absorption coefficient under three experiment energy；Utilize computer programming, By linear for the X-ray of each point in CT section selected areas (square frame in Fig. 4) under three energy AbsorptanceInput model corresponding to (3) formula also often utilizes in mathematics The simplex method of rule carries out linear optimization to model and solves, and in available model, each point is not With component group volume fractionRegion corresponding for model ash component group is found out, this portion Mineral constituent in the correspondence residue of subregion；6th step, rejecting inorganic component, further discriminate between Organic component: according to the result of calculation of the 5th step, by ash component group calculated in model Corresponding region is set as read-only, is not involved in further calculating；By the heavy oil in organic component with Bitumen is set as a component group；Unconverted matrix of coal is set as a component Group；Hole is individually set as a component group；Repeat the calculating of the 5th step, i.e. carry out such as (4) The planning of linear optimal shown in formula calculates:

$\left\{\begin{array}{c}\underset{k=1}{\overset{2}{\Σ}}{\mathrm{\μ}}^{(1,k)}{v}_n^{\left(k\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(1\right)}\\ \underset{k=1}{\overset{2}{\Σ}}{\mathrm{\μ}}^{(2,k)}{v}_n^{\left(k\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(2\right)}\\ \underset{k=1}{\overset{2}{\Σ}}{\mathrm{\μ}}^{(3,k)}{v}_n^{\left(k\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(3\right)}\\ \underset{k=0}{\overset{2}{\Σ}}{v}_n^{\left(k\right)}=1\\ 0\≤v_n^{\left(k\right)}\≤1\end{array}\right.---\left(4\right)$

The wherein the most corresponding different packet of the different value of k (=0,1,2), k=0 correspondence hole group, The corresponding unconverted matrix of coal group of k=1, k=2 correspondence heavy oil and bitumen group；Table Show the volume fraction being grouped k in the n-th simple cubic lattice；μ^(1,k)、μ^(2,k)、μ^(3,k)Represent respectively Packet k X-ray linear absorption coefficient under three CT test energy, heavy oil and Colophonium class Material group X-ray linear absorption coefficient under corresponding energy is equal to heavy oil and bitumen The meansigma methods of absorptance under corresponding energy；Represent that experiment obtains respectively The n-th simple cubic lattice three experiment energy under X-ray linear absorption coefficients；Pass through Optimum programming problem (4) formula can be solved by simplex method, tries to achieve in CT section each The volume fraction of each packet in simple cubic lattice；Difference has to utilize different colours to show in a model The distribution of machine component, it is achieved the visualization of coal directly-liquefied residue sample organic component distribution form Characterize.

Content of ashes, ash composition and ash composition in coal directly-liquefied residue sample in the first step In content, coal directly-liquefied residue sample, heavy oil and bitumen molecular formula are to be divided by industry The laboratory facilities such as analysis, elementary analysis, ash analysis obtain.In coal directly-liquefied residue sample Organic component (unconverted matrix of coal, heavy oil, bitumen) molecular formula is based on organic element Ratio is write out.Above-mentioned laboratory facilities are means commonly used in the art.

In second step, the X-ray absorption characteristic of the second each component of coal directly-liquefied residue sample is divided Analysis, is that the composition analysis result according to the first coal directly-liquefied residue sample is carried out.First coal Direct liquefaction residue sample and the second coal directly-liquefied residue sample are from the direct liquid of batch of coal Change in residue and choose, brought to reduce different batches residue sample fundamental property difference Error.

CT experimental noise is caused by CT experimental provision and experiment parameter, CT experimental provision And experiment parameter is different, CT experimental noise level is the most different, and those skilled in the art can basis Actually used device and relevant parameter determine the numerical value of CT experimental noise.

In 4th step, mineral constituent is chosen in CT section and the less region of hole is counted At last in order to reduce the uncertainty due to residue Mineral Component and large area hole as far as possible The impact that organic component CT in residue is differentiated by gap.

In 5th step, in first three equation in (3) formula use the number of approximating, be due to There is approximation by the mellow lime mineralogical composition being divided in point replacement sample of residue, utilize of the present invention Method is calculated X-ray linear absorption coefficient and the residue Minerals of sample ash component group Real X-ray linear absorption coefficient the most equal, so equation both sides are not tight Lattice are equal.This makes in (3) formulaTo solve not be simple Solving Linear, And it is belonging to mathematical linear optimal planning problem.This makes different groups in residue CT section The discriminating divided is not the linear absorption coefficient theoretical value depending on merely each component and experiment value Corresponding relation, but with after in the CT experimental data of three different-energies and (3) formula Different component in residue, as constraints, is differentiated by two formulas by linear optimal planning. So can solve the difficult problem that residue Minerals molecular formula is difficult to determine.

In 6th step, ash component group corresponding region calculated in model is set to only Read, organic component is carried out further component discriminating, is because inorganic component and organic component X-ray linear absorption coefficient difference is much larger than the difference in organic component between different component, as Fruit is disposable to all components (different organic components and different mineral groups in the 5th step Point) carry out optimization computation, then simultaneously it is difficult to organic component is mutually distinguished.Meanwhile, Residue component is grouped at twice and linear optimal planning calculates, it is possible to reduce Optimize the component number in calculating, be conducive to obtaining reliable calculating during optimization computation Result.

CT characterizing method of the present invention uses acquisition under multiple homogeneous X-raies experiment energy CT data aggregate is analyzed, and is grouped the component of coal directly-liquefied residue sample and CT at twice Differentiate, utilize the ash composition of residue to replace the mineral constituent composition in residue, by residue sample On CT picture, the discriminating of different component forms a linear optimal planning problem, by simplex This problem is solved by method, organic in can realizing cutting into slices coal directly-liquefied residue sample CT The differentiation of component and discriminating.By setting up physical model in single CT volume elements, can effectively examine Go out the small inorganic component granule in organic component.Inorganic component in model is set to read-only After again organic component is carried out packet calculate, by multiple CT experiment energy data constraint, The method utilizing linear optimal to plan can distinguish in organic component unconverted matrix of coal with Heavy oil and bitumen, reduce in residue sample inorganic component to organic component discrimination process Impact.Physical model with linear optimal planning problem as core of the present invention, can So that computational efficiency is greatly improved, can be used for the sign of a large amount of sample.Method therefor of the present invention is to recognizing Know the mode that be combined with each other of organic component in coal directly-liquefied residue, develop in new residue useful Material recovery method has great science and technology and economic implications.

Accompanying drawing explanation

Al in Fig. 1 residue₂O₃、SiO₂And CaO is relative to Fe₂O₃X-ray absorption compare image.

K in Fig. 2 residue₂O、Na₂O、P₂O₅, MgO and TiO₂Fe relatively₂O₃X-ray absorption ratio Image.

The X-ray absorption characteristic image of Fig. 3 residue component is the most unconverted matrix of coal.

The CT section obtained is reconstructed under the X-ray energy of Fig. 4 16keV.

Fig. 5 residue Minerals, organic component group, the scattergram of hole.

Fig. 6 difference organic component scattergram in residue.

Detailed description of the invention

The coal that characterizing method of the present invention can characterize different liquefaction technology scheme acquisition is direct Liquefied residue sample.Below with a certain liquefaction technology scheme obtain coal directly-liquefied residue as reality The present invention will be described in detail to execute example.This embodiment is intended merely to this is expanded on further Bright, but it is not limiting as the scope that the present invention is protected.

The CT characterizing method of a kind of coal directly-liquefied residue sample, comprises the steps: first Step, the sampling of coal directly-liquefied residue sample and pretest: in a collection of coal directly-liquefied residue Sample is chosen for organic component molecular formula, the first DCL/Direct coal liquefaction of mineral grey composition test Residue sample, and the second coal directly-liquefied residue sample for CT experiment；By experiment Means obtain the first coal directly-liquefied residue sample fundamental property test data, the direct liquid of described coal Change residue sample fundamental property test data include content of ashes in coal directly-liquefied residue sample, Unconverted matrix of coal, weight in ash composition and ash component content, coal directly-liquefied residue sample Oil and bitumen molecular formula.Infer according to coal directly-liquefied residue sample ash component content Each ash composition volume fraction in total ash；Carry out the industry of coal directly-liquefied residue sample The industry conventionally test means such as analysis, elementary analysis, ash analysis, wherein the first direct liquid of coal The fundamental property test data changing residue sample are shown in Table 1.In residue organic molecule formula, heavy oil With the molecular formula of bitumen be according to document (Gu little Hui, Zhou Ming, Shi Shidong. anthracology The molecular structure [J] of mink cell focus component in report Shenhua direct coal liquefaction residue. coal journal, 2006, 31 (1): the 76-80. little meetings of paddy, Shi Shidong, Zhou Ming. Shenhua direct coal liquefaction residue medium pitch alkene Molecular structure research [J] of component. coal journal, 2006,31 (6): 785-789.) reporting style survey Examination obtains, and unconverted matrix of coal is directly to write according to organic element ratio in the raw coal of liquefaction Go out.

Table 1 first coal directly-liquefied residue sample fundamental property

Table 2 is to infer according to coal directly-liquefied residue sample ash component content in table 1 to obtain each ash Composition volume fraction in total ash.According to estimating method, the quality of each ash composition contains Amount obtains numerical value compared with density and is the volume ratio of each ash composition, can calculate according to volume ratio The volume content of each ash composition in ash.

Table 2 is calculated each ash composition in residue and accounts for the volume fraction of total ash

According to CT device sample stage requirement, for the second coal directly-liquefied residue sample of CT experiment Suitable shape need to be milled into, it is ensured that sample surfaces does not has sharp-pointed corner angle, and used in experiment Under X-ray energy, the X-ray transmission rate of sample is at 30%-70%.The present embodiment will be used for Second coal directly-liquefied residue sample abrasive paper for metallograph one direction of CT experiment is manual to be milled into directly Footpath 4mm, the cylinder of high 0.8mm.Except cylindric, the second coal directly-liquefied residue sample is also Other shapes meeting CT device sample stage requirement can be milled into.

Second step, the X-ray absorption characteristic of the second coal directly-liquefied residue sample each ash composition are divided Analysis: calculate the second coal directly-liquefied residue sample under different x-ray energy according to formula (1) In the ratio of X-ray absorption amount of each ash composition,

$y_1=\frac{{\mathrm{\μ}}_i\left(x\right)\×V_i}{{\mathrm{\μ}}_m\left(x\right)\×V_m}---\left(1\right)$

In formula (1), i represents different ash compositions；M represents with reference to ash composition, described reference Ash composition is composition most to X-ray absorption in ash；X represents X-ray energy； μ_i(x) and μ_mX () represents ash component i respectively and is x keV with reference to ash composition at energy X-ray linear absorption coefficient；V_iAnd V_mRepresent ash component i respectively and with reference to ash composition Volume fraction；Neglect the ratio ash composition less than or equal to CT experimental noise level, Remainder ash composition；Described remainder ash composition is with reference to ash composition by one With remaining ash composition composition.

Fig. 1 and Fig. 2 is the image obtained according to formula (1).It can be observed from fig. 2 that with Fe₂O₃Compare, K₂O、Na₂O、P₂O₅, MgO and TiO₂The X-ray absorption amount caused Seldom.CT experimental noise level in view of the CT experimental provision used in this enforcement is 2%, These components (K₂O、Na₂O、P₂O₅、MgO、TiO₂) be not easily detected.So, During CT in the later stage analyzes, these components will be left in the basket.So, remainder ash composition is Fe₂O₃、Al₂O₃、SiO₂And CaO.

3rd step, the second coal directly-liquefied residue sample component packet: count according to formula (2) Calculate remainder ash composition and the X-ray line of unconverted matrix of coal under different x-ray energy The ratio of property absorptance,

$y_2=\frac{{\mathrm{\μ}}_{\mathrm{\α}}^r\left(x\right)}{{\mathrm{\μ}}_0^r\left(x\right)}---\left(2\right)$

α in formula (2) represents different remainder ash compositions,Represent residue Part of ash composition α is at the X-ray linear absorption coefficient that energy is x keV；Represent In residue, unconverted matrix of coal is at the X-ray linear absorption coefficient that energy is x keV；Make Each remainder ash composition and the X-ray line of unconverted matrix of coal under different x-ray energy Property absorptance ratio curve, is grouped remainder ash composition, and X-ray is linearly inhaled The ash that receipts coefficient curve is parallel to each other becomes to be divided into a group.

Fig. 3 is remainder ash composition (Fe in residue₂O₃、Al₂O₃、SiO₂, CaO) phase X-ray linear absorption coefficient curve to unconverted matrix of coal.For the ease of relatively different groups Divide absorptance slope of a curve, the absorptance curve of each component has been carried out entirety by figure Zoom in or out so that the absorptance curve of different component is the most close.

By Fig. 3 it can be seen that, Fe₂O₃It is parallel to each other with the absorptance curve of CaO, Al₂O₃ With SiO₂X-ray absorption coefficient curve be parallel to each other.X-ray according to different component is inhaled Receive characteristic can be divided into by remainder ash composition: a) Fe₂O₃With CaO, b) Al₂O₃With SiO₂Two component groups.

4th step, the CT experiment of coal directly-liquefied residue sample: find out between different group X-ray linear absorption coefficient curve the most uneven energy section, selects in above-mentioned energy section Take three X-ray experiment energy and carry out CT experiment respectively, it is thus achieved that multiple projection images, CT is real The imaging resolution testing projection image is a；Above-mentioned projection image is carried out CT section reconstruct, reconstruct During deduct the bright background in projection image and dark background, the distinguishable unit of minimum of CT section Size be a × a, three energy CT cut into slices in choose the three of counter sample same position CT section, chooses picture quality preferably and hole and mineral in these three CT sections Less region carries out next step and calculates, the area pixel cut out a size of e × f；

When being embodied as, the CT experiment carried out in the 4th step is in synchrotron radiation or to be provided that good Carry out on the device of good homogeneous X-ray.The CT experiment of the present invention is to synchronize at SSRF Radiation BL13W line station obtains, and its imaging resolution is a=3.7 μm, all adopts before and after imaging Collection dark background and bright background.Choose 14keV, 16keV, 20keV tri-(with sample non-hole Gap packet number is identical) X-ray experiment energy, under above three X-ray experiment energy, Gather 1080 projection images respectively.

All projection images carry out CT section reconstruct, and that has deducted in projection image in restructuring procedure is bright Background and dark background.Fig. 4 be 16keV X-ray energy under reconstruct CT section obtained, On image, minimum distinguishable unit size is a × a=3.7 μ m 3.7 μm.Fig. 4 (examine by essence Look into reference material coloured picture 4) in the corresponding different X-ray absorption coefficient of different gray values, white area The X-ray absorption coefficient value correspondence mineral that domain representation is higher, gray area represents relatively low absorption Coefficient value correspondence Organic substance.The CT section that three energy reconstruct obtain is chosen in Fig. 4 square frame Region carries out next step calculating, and the Pixel Dimensions of selected areas is: e × f=224 × 224. In selected areas, mineral distribution is less, and without obvious large scale hole.

5th step, setting up physical model, in cutting into slices CT, different component makes a distinction discriminating: model Being made up of N (N=e × f) individual simple cubic lattice, each simple cubic lattice is selected with in CT section The pixel one_to_one corresponding in region, the size of each simple cubic lattice is a × a × a, to all The linear optimal planning that simple cubic lattice is carried out as shown in (3) formula calculates:

$\left\{\begin{array}{c}\underset{c=1}{\overset{C}{\Σ}}{\mathrm{\μ}}^{(1,c)}{V}_n^{\left(c\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(1\right)}\\ \underset{c=1}{\overset{C}{\Σ}}{\mathrm{\μ}}^{(2,c)}{V}_n^{\left(c\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(2\right)}\\ \underset{c=1}{\overset{C}{\Σ}}{\mathrm{\μ}}^{(3,c)}{V}_n^{\left(c\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(3\right)}\\ \underset{c=0}{\overset{C}{\Σ}}{V}_n^{\left(c\right)}=1\\ 0\≤V_n^{\left(c\right)}\≤1\end{array}\right.---\left(3\right)$

Wherein c (=0,1,2 ... .C) different value respectively corresponding different packet, c=0 pair Answer hole group；C=1 correspondence Organic substance group, c=2,3 ... C correspondence remainder ash is divided into Ash component group；Represent the volume fraction being grouped c in the n-th simple cubic lattice；μ^(1,c)、 μ^(2,c)、μ^(3,c)Represent packet c X-ray linear absorption under three CT test energy respectively Coefficient, during c=1, μ^(1,c)、μ^(2,c)、μ^(3,c)Equal to the matrix of coal in Organic substance, heavy oil, drip Blue or green class material meansigma methods of absorptance under corresponding X-ray energy, c=2,3 ... during C, μ^(1,c)、 μ^(2,c)、μ^(3,c)Equal to each component X-ray linear absorption coefficient under corresponding energy in packet c It is multiplied by this component volume fraction in a packet, adds up summation and obtain total value, more total divided by packet c Volume fraction；Represent that the n-th simple cubic lattice that experiment obtains exists respectively X-ray linear absorption coefficient under three experiment energy；Utilize computer programming, by three Each point in CT section selected areas (square frame in examination as to substances reference material Fig. 4) under energy X-ray linear absorption coefficientThe model also profit that input (3) formula is corresponding By simplex method conventional in mathematics, model is carried out linear optimization to solve, available model The different component group volume fraction of middle each pointBy region corresponding for model ash component group Finding out, this subregion represents the mineral constituent in residue.

Wherein N=e × f is N=224 × 224, and the size of each simple cubic lattice is 3.7×3.7×3.7μm³.(3) in formula, C=3；The most corresponding hole group of c (=0,1,2,3), Organic substance group, Al₂O₃With SiO₂Group and Fe₂O₃With CaO group.

Non-hole group c (=1,2,3) X-ray linear absorption system under three experiment energy Number value is as shown in table 3:

Each component group linear absorption coefficient value in table 3 linear optimization calculating for the first time

Wherein, during c=1, corresponding μ^(1,c)、μ^(2,c)、μ^(3,c)Value is unconverted coal base in residue Matter, heavy oil, the meansigma methods of bitumen X-ray linear absorption coefficient, c=2 is when 3, right The μ answered^(1,c)、μ^(2,c)、μ^(3,c)Value is each component X-ray linear absorption coefficient in component group Volumetrically weighted average.Value can reconstruct under three CT test energy In the CT section obtained, in boxed area as shown in Figure 4, each point reads, and utilizes computer Programming, by μ^(1,c)、μ^(2,c)、μ^(3,c)、Numerical value input (3) formula corresponding Model and utilize the method for simplex that model is carried out linear optimization to solve, available model The different component group volume fraction of middle each point.

Fig. 5 (examination as to substances reference material coloured picture 5) be (3) formula is calculated after the residue that obtains Minerals, organic component group, the distribution situation of hole.Figure Minerals group is all used blue aobvious Show, Organic substance group and hole group red display, in figure the display intensity proportional of each point color in Each component is in the calculated volume fraction in this position.

6th step, rejecting inorganic component, further discriminate between organic component: tie according to the calculating of the 5th step Really, ash component group corresponding region calculated in model is set as read-only, be not involved in into The calculating of one step.Heavy oil in organic component and bitumen are set as a component group； Unconverted matrix of coal is set as a component group；Hole is individually set as a component group； Repeat the calculating of the 5th step, i.e. carry out linear optimal planning as shown in (4) formula and calculate:

$\left\{\begin{array}{c}\underset{k=1}{\overset{2}{\Σ}}{\mathrm{\μ}}^{(1,k)}{v}_n^{\left(k\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(1\right)}\\ \underset{k=1}{\overset{2}{\Σ}}{\mathrm{\μ}}^{(2,k)}{v}_n^{\left(k\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(2\right)}\\ \underset{k=1}{\overset{2}{\Σ}}{\mathrm{\μ}}^{(3,k)}{v}_n^{\left(k\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(3\right)}\\ \underset{k=0}{\overset{2}{\Σ}}{v}_n^{\left(k\right)}=1\\ 0\≤v_n^{\left(k\right)}\≤1\end{array}\right.---\left(4\right)$

The wherein the most corresponding different packet of the different value of k (=0,1,2), k=0 correspondence hole group, The corresponding unconverted matrix of coal group of k=1, k=2 correspondence heavy oil and bitumen group；Table Show the volume fraction being grouped k in the n-th simple cubic lattice；μ^(1,k)、μ^(2,k)、μ^(3,k)Represent respectively Packet k X-ray linear absorption coefficient under three CT test energy, heavy oil and Colophonium class Material group X-ray linear absorption coefficient under corresponding energy is equal to heavy oil and bitumen The meansigma methods of absorptance under corresponding energy；Represent that experiment obtains respectively The n-th simple cubic lattice three experiment energy under X-ray linear absorption coefficients；Pass through Optimum programming problem (4) formula can be solved by simplex method, tries to achieve in CT section each The volume fraction of each packet in simple cubic lattice；Difference has to utilize different colours to show in a model The distribution of machine component, it is achieved the visualization of coal directly-liquefied residue sample organic component distribution form Characterize.

In being embodied as, μ^(1,k)、μ^(2,k)、μ^(3,k)Value as shown in table 4.

Each component group linear absorption coefficient value in table 4 second time linear optimization calculating

Utilize computer programming, numerical value in table 4 and three CT are tested energy reformatted slices The X-ray of middle Fig. 5 (examination as to substances reference material coloured picture 5) red area correspondence position is linear AbsorptanceSubstitute in (4) formula institute representation model, to Fig. 5 institute diagram In sheet, red area carries out optimization computation, obtains heavy oil as shown in Figure 6 and bitumen Group and the scattergram of unconverted matrix of coal group.In Fig. 6 (examination as to substances reference material coloured picture 6) The unconverted matrix of coal of red expression, green expression heavy oil and bitumen, each point color shows Show intensity proportional volume fraction of each component in each simple cubic lattice, figure does not shows hole Group and the distribution of Fig. 5 Minerals group.

Claims (1)

1. the CT characterizing method of a coal directly-liquefied residue sample, it is characterised in that include as Lower step: the first step, the sampling of coal directly-liquefied residue sample and pretest: in a collection of coal Direct liquefaction residue sample is chosen for organic component molecular formula, the of mineral grey composition test One coal directly-liquefied residue sample, and the second coal directly-liquefied residue sample for CT experiment Product；The first coal directly-liquefied residue sample fundamental property test data are obtained by laboratory facilities, Described coal directly-liquefied residue sample fundamental property test data include coal directly-liquefied residue sample In product in content of ashes, ash composition and ash component content, coal directly-liquefied residue sample not Convert matrix of coal, heavy oil and bitumen molecular formula；According to coal directly-liquefied residue sample ash Component content is divided to infer each ash composition volume fraction in total ash；Second step, second The X-ray absorption specificity analysis of coal directly-liquefied residue sample each ash composition: according to formula (1) each ash composition in the second coal directly-liquefied residue sample is calculated under different x-ray energy The ratio of X-ray absorption amount,

$y_1=\frac{{\mathrm{\μ}}_i\left(x\right)\×V_i}{{\mathrm{\μ}}_m\left(x\right)\×V_m}---\left(1\right)$

In formula (1), i represents different ash compositions；M represents with reference to ash composition, described reference Ash composition is composition most to X-ray absorption in ash；X represents X-ray energy； μ_i(x) and μ_mX () represents ash component i respectively and is x keV with reference to ash composition at energy X-ray linear absorption coefficient；V_iAnd V_mRepresent ash component i respectively and with reference to ash composition Volume fraction；Neglect the ratio ash composition less than or equal to CT experimental noise level, Remainder ash composition；Described remainder ash composition is with reference to ash composition by one With remaining ash composition composition；3rd step, the second coal directly-liquefied residue sample component packet: Remainder ash composition and unconverted coal under different x-ray energy is calculated according to formula (2) The ratio of the X-ray linear absorption coefficient of substrate,

$y_2=\frac{{\mathrm{\μ}}_{\mathrm{\α}}^r\left(x\right)}{{\mathrm{\μ}}_0^r\left(x\right)}---\left(2\right)$

α in formula (2) represents different remainder ash compositions,Represent residue Part of ash composition α is at the X-ray linear absorption coefficient that energy is x keV；Represent In residue, unconverted matrix of coal is at the X-ray linear absorption coefficient that energy is x keV；Make Each remainder ash composition and the X-ray line of unconverted matrix of coal under different x-ray energy Property absorptance ratio curve, is grouped remainder ash composition, and X-ray is linearly inhaled The ash that receipts coefficient curve is parallel to each other becomes to be divided into a group；4th step, the second direct liquid of coal Change the CT experiment of residue sample: find out the X-ray linear absorption coefficient between different group bent Line the most uneven energy section, chooses three X-ray experiment energy in above-mentioned energy section Amount carries out CT experiment respectively, it is thus achieved that multiple projection images, and the imaging of CT experimental projection picture is differentiated Rate is a；Above-mentioned projection image is carried out CT section reconstruct, restructuring procedure is deducted in projection image Bright background and dark background, the size of the distinguishable unit of minimum of CT section is a × a, The CT section of three energy is chosen three CT sections of counter sample same position, at this Picture quality is chosen preferably and under hole and the less region of mineral carry out in three CT section One step calculates, the area pixel cut out a size of c × d；

5th step, setting up physical model, in cutting into slices CT, different component makes a distinction discriminating: model Being made up of N (N=e × f) individual simple cubic lattice, each simple cubic lattice is selected with in CT section The pixel one_to_one corresponding in region, the size of each simple cubic lattice is a × a × a, to all The linear optimal planning that simple cubic lattice is carried out as shown in (3) formula calculates:

$\left\{\begin{array}{c}\underset{c=1}{\overset{C}{\Σ}}{\mathrm{\μ}}^{(1,c)}{V}_n^{\left(c\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(1\right)}\\ \underset{c=1}{\overset{C}{\Σ}}{\mathrm{\μ}}^{(2,c)}{V}_n^{\left(c\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(2\right)}\\ \underset{c=1}{\overset{C}{\Σ}}{\mathrm{\μ}}^{(3,c)}{V}_n^{\left(c\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(3\right)}\\ \underset{c=0}{\overset{C}{\Σ}}{V}_n^{\left(c\right)}=1\\ 0\≤V_n^{\left(c\right)}\≤1\end{array}\right.---\left(3\right)$

Wherein c (=0,1,2 ... .C) different value respectively corresponding different packet, c=0 pair Answer hole group；C=1 correspondence Organic substance group, c=2,3 ... C correspondence remainder ash is divided into Ash component group；Represent the volume fraction being grouped c in the n-th simple cubic lattice；μ^(1,c)、 μ^(2,c)、μ^(3,c)Represent packet c X-ray linear absorption under three CT test energy respectively Coefficient, during c=1, μ^(1,c)、μ^(2,c)、μ^(3,c)Equal to the matrix of coal in Organic substance, heavy oil, drip Blue or green class material meansigma methods of absorptance under corresponding X-ray energy, c=2,3 ... during C, μ^(1,c)、 μ^(2,c)、μ^(3,c)Equal to each component X-ray linear absorption coefficient under corresponding energy in packet c It is multiplied by this component volume fraction in a packet, adds up summation and obtain total value, more total divided by packet c Volume fraction；Represent that the n-th simple cubic lattice that experiment obtains exists respectively X-ray linear absorption coefficient under three experiment energy；Utilize computer programming, by three The X-ray linear absorption coefficient of each point in CT section selected areas under energy Input model corresponding to (3) formula also utilizes simplex method conventional in mathematics to model Carry out linear optimization to solve, the different component group volume fraction of each point in available model Region corresponding for model ash component group is found out, the ore deposit in this subregion correspondence residue Thing component；6th step, rejecting inorganic component, further discriminate between organic component: according to the 5th step Result of calculation, ash component group corresponding region calculated in model is set as read-only, It is not involved in further calculating；Heavy oil in organic component and bitumen are set as one Component group；Unconverted matrix of coal is set as a component group；Hole is individually set as one Component group；Repeat the calculating of the 5th step, i.e. carry out linear optimal planning meter as shown in (4) formula Calculate:

$\left\{\begin{array}{c}\underset{k=1}{\overset{2}{\Σ}}{\mathrm{\μ}}^{(1,k)}{v}_n^{\left(k\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(1\right)}\\ \underset{k=1}{\overset{2}{\Σ}}{\mathrm{\μ}}^{(2,k)}{v}_n^{\left(k\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(2\right)}\\ \underset{k=1}{\overset{2}{\Σ}}{\mathrm{\μ}}^{(3,k)}{v}_n^{\left(k\right)}\≈{\widehat{\mathrm{\μ}}}_n^{\left(3\right)}\\ \underset{k=0}{\overset{2}{\Σ}}{v}_n^{\left(k\right)}=1\\ 0\≤v_n^{\left(k\right)}\≤1\end{array}\right.---\left(4\right)$

The wherein the most corresponding different packet of the different value of k (=0,1,2), k=0 correspondence hole group, The corresponding unconverted matrix of coal group of k=1, k=2 correspondence heavy oil and bitumen group；Table Show the volume fraction being grouped k in the n-th simple cubic lattice；μ^(1,k)、μ^(2,k)、μ^(3,k)Represent respectively Packet k X-ray linear absorption coefficient under three CT test energy, heavy oil and Colophonium class Material group X-ray linear absorption coefficient under corresponding energy is equal to heavy oil and bitumen The meansigma methods of absorptance under corresponding energy；Represent that experiment obtains respectively The n-th simple cubic lattice three experiment energy under X-ray linear absorption coefficients；Pass through Optimum programming problem (4) formula can be solved by simplex method, tries to achieve in CT section each The volume fraction of each packet in simple cubic lattice；Difference has to utilize different colours to show in a model The distribution of machine component, it is achieved the visualization of coal directly-liquefied residue sample organic component distribution form Characterize.