WO2008025246A1 - Procédé de détermination de la teneur en carbone d'un catalyseur solide - Google Patents

Procédé de détermination de la teneur en carbone d'un catalyseur solide Download PDF

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Publication number
WO2008025246A1
WO2008025246A1 PCT/CN2007/002536 CN2007002536W WO2008025246A1 WO 2008025246 A1 WO2008025246 A1 WO 2008025246A1 CN 2007002536 W CN2007002536 W CN 2007002536W WO 2008025246 A1 WO2008025246 A1 WO 2008025246A1
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WO
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Prior art keywords
carbon content
catalyst
absorbance
solid catalyst
diffuse reflectance
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Application number
PCT/CN2007/002536
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English (en)
Chinese (zh)
Inventor
Zhongmin Liu
Jinling Zhang
Lei Xu
Cuiyu Yuan
Bing Li
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Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences
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Application filed by Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences filed Critical Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences
Publication of WO2008025246A1 publication Critical patent/WO2008025246A1/fr

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    • 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

Definitions

  • the present invention relates to a method for determining the carbon content of a catalyst in industries such as coal chemical, methanol to olefin, petrochemical, petroleum refining, and the like, and more particularly to a method for rapidly determining the carbon content of a solid catalyst. Background technique
  • Solid Catalyst During use, carbon may deposit on the surface of the catalyst or in the pores. Severe carbon deposits may affect the catalytic performance of the catalyst. Therefore, it is necessary to determine the carbon content in the solid catalyst to understand the carbon deposition on the catalyst.
  • the determination methods of carbon content of solid catalysts are as follows: 1. Thermogravimetric method, the amount of total carbon deposits (the sum of C and H); 2. The carbon fixation method of steel (national standard GB/T 223.69-1997), In a tubular furnace, the carbon on the known weight of the catalyst is completely combusted to generate carbon dioxide under high temperature and air, and the burned gas is passed through a standard potassium hydroxide solution, and the volume difference is the volume of carbon dioxide, and the carbon content on the catalyst is obtained by conversion; 3. The carbon dioxide generated by combustion is dissolved into the alkali solution to cause a change in the conductivity of the solution. The carbon content of the catalyst is obtained by using a standard external standard of carbon content; 4.
  • Infrared is used as a detection means.
  • the carbon dioxide generated by combustion absorbs infrared energy of a certain wavelength, and its absorption energy is proportional to the concentration of carbon, and the carbon content of the catalyst can be obtained.
  • Gas chromatography detection method of combustion gas, Xu Chunming, etc. (Chinese patent application) No. 96211983.0) developed a carbon fixation method, which is characterized by column separation and thermal conductivity detector in gas chromatography. Given catalyst soot combustion amount of carbon dioxide, the carbon content on the catalyst thus obtained.
  • thermogravimetric method is complicated.
  • the general operations such as the steel carbon fixation method and the conductivity method are complicated, the measurement time is long, and the standard lye is periodically replaced.
  • Infrared analysis has high analytical accuracy, is generally applicable to line analysis, and is expensive.
  • Chromatography requires standard gas for quantification, and post-treatment requires high precision.
  • the carbon content on the catalyst has a great influence on the activity and selectivity of the catalyst, especially in the industrial production of coal chemical, methanol to olefin, petrochemical, petroleum catalytic cracking, petroleum refining and other industrial production, the carbon content of the catalyst is determined in time to guide the production. Important role. Summary of the invention
  • the present invention provides a method for rapidly determining the carbon content of a solid catalyst, the method comprising the steps of:
  • the carbon content of the solid catalyst is obtained as a function of the absorbance obtained and the carbon content obtained in 1) as a function of absorbance or diffuse reflectance.
  • the absorbance or diffuse reflectance is an arithmetic calculation of the absorbance or diffuse reflectance of a single wavelength, or the absorbance or diffuse reflectance of a plurality of wavelengths.
  • the solid catalyst is used directly for the determination.
  • the solid catalyst is uniformly mixed with a standard for ultraviolet diffuse reflection and then measured.
  • catalysts of the same nature have different functional relationships after carbon deposition through different reaction processes.
  • solid catalysts of the same nature have a different functional relationship after the reaction and after regeneration, when used in a circulating fluidization reaction.
  • the measuring method provided by the invention is suitable for measuring the carbon content of the catalyst in the industries of coal chemical industry, methanol to olefins, petrochemical industry and petroleum refining.
  • Figure 2 is a linear relationship between different carbon content and absorbance of the catalyst in Example 2 of the present invention. detailed description
  • the invention uses ultraviolet diffuse reflectance spectroscopy to determine the carbon content of a solid catalyst.
  • Some catalysts with known carbon content and the same properties are subjected to ultraviolet diffuse reflectance spectroscopy.
  • the absorbance and carbon content of a certain wavelength are selected for regression analysis, and the regression equation and the determination coefficient R 2 can be obtained. Multiple wavelengths can also be selected.
  • the absorbance is calculated by the formula, and the obtained result and the carbon content of the catalyst are subjected to regression analysis to obtain a regression equation and a coefficient of determination R 2 . The larger R 2 or the closer to 1 the better the degree of fit.
  • the catalyst with the same carbon content and the same properties is subjected to ultraviolet diffuse reflectance spectroscopy, and the carbon content of the catalyst can be directly obtained according to the regression analysis equation.
  • ultraviolet diffuse reflectance spectroscopy such as barium sulfate
  • the regression analysis equation obtained may be different due to the difference in the nature and content of the catalyst carbon after the reaction and the regeneration. Catalysts of the same nature may undergo carbon deposition after different reactions, and the regression analysis equations produced by the carbon content and absorbance of the catalyst may also be different.
  • the invention is described in detail below by means of examples, but the invention is not limited to the examples.
  • Dalian Institute of Chemical Physics developed a catalyst for methanol to olefins.
  • the main preparation process was to prepare SAPO-34 molecular sieve raw powder, kaolin, silica sol and water in a ratio of 1: 1.37: 1.87: 3.54.
  • the slurry has a solids content of 30%.
  • the slurry is spray dried and dried to obtain a microsphere catalyst, and then at 550
  • the mixture was calcined in air for 5 hours to obtain a methanol-to-olefin microsphere fluidization catalyst.
  • the reaction temperature is 480 ° C
  • the regeneration temperature is 650 ° C
  • the total catalyst loading is
  • Example 2 Using the catalyst and the reaction apparatus and the reaction and regeneration conditions of Example 1, the catalyst samples under different conditions, that is, the samples of different regenerated catalyst carbon contents, were taken at the lower end of the regenerator. The carbon content of each sample was measured by a thermogravimetric method, and each sample was subjected to ultraviolet diffuse reflection measurement. The apparatus and measurement conditions were the same as those in Example 1, and the results obtained are shown in Table 3.
  • thermogravimetric result of the catalyst is that if the thermogravimetric result is the true value, the absolute error between the result of the ultraviolet diffuse reflection measurement and the true value is t%, and the relative error is 0.67%.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

Un procédé de détermination de la teneur en carbone d'un catalyseur solide, faisant intervenir une spectroscopie à réfléchissement diffusé par ultraviolets afin de déterminer la capacité d'absorption de l'échantillon avant d'en obtenir la teneur en carbone. L'équation de régression est d'abord obtenue par la teneur en carbone de l'échantillon connu et sa capacité d'absorption. Une teneur en carbone inconnue de l'échantillon est ensuite déterminée afin d'obtenir sa capacité d'absorption par spectroscopie de réfléchissement à diffusion par ultraviolets. La teneur en carbone du catalyseur est obtenue au moyen de l'équation de régression.
PCT/CN2007/002536 2006-08-23 2007-08-22 Procédé de détermination de la teneur en carbone d'un catalyseur solide WO2008025246A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2006101125546A CN101131355B (zh) 2006-08-23 2006-08-23 一种快速测定固体催化剂碳含量的方法
CN200610112554.6 2006-08-23

Publications (1)

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WO2008025246A1 true WO2008025246A1 (fr) 2008-03-06

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Publication number Priority date Publication date Assignee Title
CN108489909B (zh) * 2018-02-12 2020-08-28 浙江大学 一种甲醇制烯烃过程的催化剂积碳量在线检测装置与方法
CN110514600A (zh) * 2019-09-05 2019-11-29 内蒙古中煤蒙大新能源化工有限公司 一种mto催化剂碳含量的测定方法
CN110596044A (zh) * 2019-09-16 2019-12-20 中国神华煤制油化工有限公司 用于催化剂表面碳含量的测定方法及应用
CN113075148B (zh) * 2021-03-22 2023-06-16 久泰能源(准格尔)有限公司 一种mto工艺中催化剂表面碳含量的测定方法

Citations (4)

* Cited by examiner, † Cited by third party
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
JPH08128947A (ja) * 1994-10-31 1996-05-21 Mitsubishi Heavy Ind Ltd 灰中未燃炭素分析法
EP0714023A2 (fr) * 1994-11-25 1996-05-29 Evn Energie-Versorgung Niederösterreich Aktiengesellschaft Méthode et dispositif pour l'évaluation de la teneur en charbon de cendre, élément pour la déviation du faisceau pour cela et son procédé de fabrication
JPH1090185A (ja) * 1996-09-18 1998-04-10 Sumika Bunseki Center:Kk 炭素材の分析方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
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
JPH08128947A (ja) * 1994-10-31 1996-05-21 Mitsubishi Heavy Ind Ltd 灰中未燃炭素分析法
EP0714023A2 (fr) * 1994-11-25 1996-05-29 Evn Energie-Versorgung Niederösterreich Aktiengesellschaft Méthode et dispositif pour l'évaluation de la teneur en charbon de cendre, élément pour la déviation du faisceau pour cela et son procédé de fabrication
JPH1090185A (ja) * 1996-09-18 1998-04-10 Sumika Bunseki Center:Kk 炭素材の分析方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LIN L. ET AL.: "Effect of carbon content on Photocatalytic Activity of C/TiO2 Composite", CHINESE JOURNAL OF CATALYSIS, vol. 27, no. 1, January 2006 (2006-01-01), pages 49 *

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CN101131355A (zh) 2008-02-27

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