CN101131355B - Method for fast measuring carbon content in solid catalyst - Google Patents
Method for fast measuring carbon content in solid catalyst Download PDFInfo
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- CN101131355B CN101131355B CN2006101125546A CN200610112554A CN101131355B CN 101131355 B CN101131355 B CN 101131355B CN 2006101125546 A CN2006101125546 A CN 2006101125546A CN 200610112554 A CN200610112554 A CN 200610112554A CN 101131355 B CN101131355 B CN 101131355B
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- carbon content
- absorbance
- catalyzer
- drs
- regression analysis
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 11
- 238000002835 absorbance Methods 0.000 claims abstract description 21
- 238000004458 analytical method Methods 0.000 claims description 13
- 238000012417 linear regression Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 5
- 239000012925 reference material Substances 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000000611 regression analysis Methods 0.000 abstract description 5
- 238000001055 reflectance spectroscopy Methods 0.000 abstract 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000003556 assay Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005504 petroleum refining Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000003134 recirculating effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007811 spectroscopic assay Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen potassium oxide Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
Abstract
A rapid determination method of carbon content in solid catalyst, the method use UV diffuse reflectance spectroscopy to detect the absorbance of samples, can directly obtain the carbon content in catalyst. First, according to the carbon content and absorbance of known samples to obtain regression analysis equation of the two, then the catalyst with unknown carbon content is tested for UV diffuse reflectance spectroscopy and get corresponding absorbance, according to regression analysis equation can directly know the carbon content in catalyst.
Description
Technical field
The present invention relates to a kind of mensuration that is used for industries such as Coal Chemical Industry, methanol-to-olefins, petrochemical complex, petroleum refining to carbon content on the catalyzer, specifically, relate to a kind of method of fast measuring carbon content in solid catalyst.
Background technology
The assay method of carbon content in solid catalyst mainly contains at present: 1, thermogravimetry (TG) obtains the sedimental amount of whole carbon distributions (C, H summation); 2, iron and steel is decided carbon method (standard GB/T 223.69-1997), in tubular furnace, under the high temperature blowing air condition carbon perfect combustion on the catalyzer of known weight is generated carbon dioxide, gas after the burning is passed through the standard hydrogen potassium oxide solution, volume differences is the carbon dioxide volume, obtains carbon content on the catalyzer through converting; 3, the carbon dioxide that utilizes the burning back to generate is dissolved into the variation that alkali lye causes electrical conductivity of solution, and the reference material external standard by with known carbon content obtains coke on regenerated catalyst.4, according to standard GB/T7730.5-2000, utilize infrared as detection means, the infrared energy of the carbon dioxide absorption specific wavelength that burning back generates, its absorption can be directly proportional with the concentration of carbon, can obtain carbon content on the catalyzer.5, burning gases gas chromatographic detection method, Xu Chunming etc. (Chinese patent application number 96211983.0) develop a kind of carbon determination method, promptly utilize chromatographic column separation and thermal conductivity detector (TCD) detection in the gas chromatography, the amount of carbon distribution burning generation carbon dioxide on the catalyzer can be measured, thereby carbon content on the catalyzer can be obtained.
In the above-mentioned various assay method, it is complicated that iron and steel is decided general operations such as carbon method and electrical conductivity method, and minute is longer, and need periodic replacement standard alkali lye.The infrared analysis analysis precision is higher, generally is useful in line analysis, and equipment is expensive.Chromatography needs calibrating gas to carry out quantitatively, and aftertreatment needs precision higher.
Because carbon content is bigger to catalyst activity, selectivity influence on the catalyzer, measure timely and accurately in commercial production such as Coal Chemical Industry, methanol-to-olefins, petrochemical complex, petroleum catalytic cracking, petroleum refining especially that carbon content plays an important role to instructing to produce on the catalyzer.
Summary of the invention
The object of the present invention is to provide a kind of method of fast measuring carbon content in solid catalyst.
For achieving the above object, the method of fast measuring carbon content in solid catalyst provided by the invention, the sample at first known to carbon content, that character is identical carries out uv drs and measures, obtain the absorbance of wavelength correspondence, and carbon content and absorbance made the linear regression analysis equation, then unknown carbon content, catalyzer that character is identical are made uv drs spectrum and obtain absorbance, directly obtain carbon content with its absorbance correspondence according to described linear regression analysis equation.
Described method, wherein absorbance is the absorbance of single wavelength, or the formula of the absorbance of a plurality of wavelength calculates.
Described method, wherein testing sample is directly to measure.
Described method, wherein testing sample evenly mixes back mensuration with uv drs with reference material.
Described method, wherein carbon distribution after the catalyzer of the same nature process differential responses process has different linear regression analysis equations.
Described method, wherein the solid catalyst of same nature has different linear regression analysis equations after its reaction with after the regeneration when being used for ciculation fluidized reaction.
Assay method provided by the invention is applicable in the industries such as Coal Chemical Industry, methanol-to-olefins, petrochemical complex, petroleum refining the mensuration to carbon content on the catalyzer.
Description of drawings
Fig. 1 is the linear relationship of the different carbon content of catalyzer and absorbance in the embodiment of the invention 1.
Fig. 2 is the linear relationship of the different carbon content of catalyzer and absorbance in the embodiment of the invention 2.
Embodiment
The present invention adopts uv drs spectrographic determination carbon content in solid catalyst.Some at first known to carbon content, that character is identical catalyzer carry out the uv drs spectroscopic assay, and the absorbance and the carbon content of selected a certain wavelength are done regretional analysis, can obtain regression equation and coefficient of determination R
2Also can select the absorbance of a plurality of wavelength, it be carried out formula calculate, the result that it obtains and the carbon content of catalyzer are done regretional analysis, obtain regression equation and coefficient of determination R
2R
2It is good more to approach 1 fitting degree more greatly or more.Then unknown carbon content, catalyzer that character is identical are carried out the uv drs spectroscopic assay,, can directly obtain coke on regenerated catalyst according to regression analysis equation.Carry out catalyzer when measuring with uv drs, can add the reference material that uv drs spectrum uses (as barium sulphate etc.) as required, evenly mix, measure behind the compressing tablet.If the catalyzer of same nature carries out ciculation fluidized reaction, because the character of the catalyst carbon after reaction back and the regeneration and content etc. have certain difference, therefore resulting regression analysis equation also is different.The catalyzer of same nature is through carbon distribution after the differential responses, and the carbon content of catalyzer is different with the regression analysis equation that absorbance is produced.
By the following examples the present invention is made detailed description, but the present invention is not limited to these embodiment.
Dalian Chemical Physics Research Institute's development methanol-to-olefins catalyzer, the sample of different carbon contents is got in the recirculating fluidized bed reaction in the reactor lower end.Adopt the method for thermogravimetric that the carbon content of each sample is measured, and each sample is carried out uv drs measure, what obtain the results are shown in Table 1.
The carbon content of table 1 catalyzer and uv drs measurement result
To absorbance A
4Make linear relationship with carbon content, obtain equation of linear regression and coefficient of determination, the results are shown in Figure 1.
Unknown carbon content catalyzer D10 carries out uv drs and measures, and the results are shown in Table 2.Again according to equation of linear regression y=6.0709x+0.7184, can obtain directly that carbon content is 6.23wt% on the catalyzer.The thermogravimetric result of this catalyzer is 6.27%, and as being actual value with the thermogravimetric result, the result that uv drs is measured and the absolute error of actual value are 0.04wt%, and relative error is 0.64%.
The unknown carbon content catalyzer of table 2 uv drs measurement result
Dalian Chemical Physics Research Institute's development methanol-to-olefins catalyzer, the sample of different carbon contents is got in the recirculating fluidized bed reaction in the regenerator lower end.Adopt the method for thermogravimetric that the carbon content of each sample is measured, and each sample is carried out uv drs measure, what obtain the results are shown in Table 3.
The carbon content of table 3 catalyzer and uv drs measurement result
To absorbance A
4Make linear relationship with carbon content, obtain equation of linear regression and coefficient of determination, the results are shown in Figure 2.
Unknown carbon content catalyzer D21 carries out uv drs and measures, and the results are shown in Table 4.Can obtain directly according to equation of linear regression y=19.18x-1.1589 again that carbon content is 1.50wt% on the catalyzer.The thermogravimetric result of this catalyzer is 1.51%, and as being actual value with the thermogravimetric result, the result that uv drs is measured and the absolute error of actual value are 0.01wt%, and relative error is 0.67%.
The unknown carbon content catalyzer of table 4 uv drs measurement result
Claims (3)
1. the method for a fast measuring carbon content in solid catalyst, the sample at first known to carbon content, that character is identical adopts the light source of single wavelength or a plurality of wavelength to carry out uv drs and measures, obtain the absorbance of each wavelength correspondence, and carbon content and absorbance made the linear regression analysis equation, then the identical catalyzer testing sample of unknown carbon content, character is directly measured or evenly mixed the back with uv drs with reference material and measure its uv drs spectrum and obtain absorbance, directly obtain carbon content with its absorbance correspondence according to the linear regression analysis equation.
2. method according to claim 1, wherein, carbon distribution after the catalyzer of the same nature process differential responses process has different linear regression analysis equations.
3. method according to claim 1, wherein, the solid catalyst of same nature has different linear regression analysis equations after its reaction with after the regeneration when being used for ciculation fluidized reaction.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101125546A CN101131355B (en) | 2006-08-23 | 2006-08-23 | Method for fast measuring carbon content in solid catalyst |
| PCT/CN2007/002536 WO2008025246A1 (en) | 2006-08-23 | 2007-08-22 | Method for determinating the carbon content of solid catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101125546A CN101131355B (en) | 2006-08-23 | 2006-08-23 | Method for fast measuring carbon content in solid catalyst |
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| CN101131355A CN101131355A (en) | 2008-02-27 |
| CN101131355B true CN101131355B (en) | 2010-09-22 |
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| WO (1) | WO2008025246A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108489909B (en) * | 2018-02-12 | 2020-08-28 | 浙江大学 | Device and method for online detection of carbon deposition amount of catalyst in methanol-to-olefin process |
| CN110514600A (en) * | 2019-09-05 | 2019-11-29 | 内蒙古中煤蒙大新能源化工有限公司 | A kind of measuring method of MTO catalyst carbon content |
| CN110596044A (en) * | 2019-09-16 | 2019-12-20 | 中国神华煤制油化工有限公司 | Method for measuring carbon content on surface of catalyst and application |
| CN113075148B (en) * | 2021-03-22 | 2023-06-16 | 久泰能源(准格尔)有限公司 | Method for measuring carbon content of catalyst surface in MTO process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3232711A (en) * | 1962-08-17 | 1966-02-01 | Gulf Research Development Co | Carbon-on-catalyst analytic apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3457749B2 (en) * | 1994-10-31 | 2003-10-20 | 三菱重工業株式会社 | Method for analyzing unburned carbon in ash |
| ES2202347T3 (en) * | 1994-11-25 | 2004-04-01 | Evn Ag | PROCEDURE AND DEVICE FOR DETERMINING THE CONTENT OF ASH CARBON. |
| JPH1090185A (en) * | 1996-09-18 | 1998-04-10 | Sumika Bunseki Center:Kk | Method for analyzing carbon material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3232711A (en) * | 1962-08-17 | 1966-02-01 | Gulf Research Development Co | Carbon-on-catalyst analytic apparatus |
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| Title |
|---|
| 赵永祥.负载型贵金属催化剂的制备化学－载体等电点对Pd/Al2O3催化剂结构与催化性能的影响.分子催化.1994,8(1),29-30. * |
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| CN101131355A (en) | 2008-02-27 |
| WO2008025246A1 (en) | 2008-03-06 |
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Owner name: SYN ENERGY TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES Effective date: 20111130 |
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Effective date of registration: 20111130 Address after: 506 room 38, building B, Xi'an Tengfei innovation center, No. six, 710075 hi tech Road, Xi'an hi tech Zone, Shaanxi, China Patentee after: SYN Energy Technology Co., Ltd. Address before: 116023 Zhongshan Road, Liaoning, No. 457, Patentee before: Dalian Institute of Chemical Physics, Chinese Academy of Sciences |