CN107540011A - A kind of catalyst of high-specific surface area, its preparation method and application - Google Patents
A kind of catalyst of high-specific surface area, its preparation method and application Download PDFInfo
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- CN107540011A CN107540011A CN201610465428.2A CN201610465428A CN107540011A CN 107540011 A CN107540011 A CN 107540011A CN 201610465428 A CN201610465428 A CN 201610465428A CN 107540011 A CN107540011 A CN 107540011A
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Abstract
The invention discloses a kind of catalyst containing zinc fluoride of the high-specific surface area for exchange chloride for fluoride, its specific surface area is 80~180m2/ g, pore volume are 0.15~0.50cm3, aperture be
Description
Technical field
The present invention relates to a kind of metal fluoride for catalytic reaction, more particularly to a kind of fluorination of high-specific surface area
Zinc catalyst.
Background technology
Zinc fluoride is widely used in ceramic glaze, electroplated, wood impregnant, brazing flux as a kind of conventional industrial chemicals
And analytical reagent etc..Preparation for zinc fluoride, prior art essentially disclose two kinds：(1) with zinc carbonate and excessive hot hydrogen
Fluoric acid is raw material, and the zinc fluoride crystal of White-opalescent is separated out after reaction, then through being heated under conditions of 800 DEG C, isolation aqueous vapor
To anhydrous zinc fluoride；(2) zinc oxide is gradually added into excessive hydrofluoric acid with water mixing batter, separates out white zinc fluoride crystallization, then
Evaporation drying can obtain anhydrous zinc fluoride.
Existing preparation method is only capable of accessing conventional zinc fluoride, can not be exchanged as catalyst applied to fluorine chlorine
Reaction.It is therefore desirable to develop a kind of new zinc fluoride that can be applied to exchange chloride for fluoride.
The content of the invention
It is an object of the invention to provide a kind of catalyst of high-specific surface area, it can be used in exchange chloride for fluoride.
The present invention adopts the following technical scheme that：
A kind of catalyst of high-specific surface area, for exchange chloride for fluoride, the catalyst contains fluorination zinc catalyst, and
The specific surface area for being fluorinated zinc catalyst is 80~180m2/ g, pore volume are 0.15~0.50cm3, aperture be
Fluorination zinc catalyst provided by the invention, its specific surface area are 80~180m2/g.Preferably, the zinc fluoride
The specific surface area of catalyst is 120~180m2/g.It may further be preferable that the specific surface area of the fluorination zinc catalyst is 140
~180m2/g。
Fluorination zinc catalyst provided by the invention, its pore volume are 0.15~0.50cm3.Preferably, the zinc fluoride is urged
The pore volume of agent is 0.28~0.50cm3.It may further be preferable that the pore volume of the fluorination zinc catalyst for 0.40~
0.50cm3。
Fluorination zinc catalyst provided by the invention, its aperture arePreferably, the fluorination zinc catalyst
Aperture isIt may further be preferable that the aperture of the fluorination zinc catalyst is
The catalyst of high-specific surface area provided by the invention, can also be further containing fluorination chrome catalysts.When described
When catalyst contains fluorination zinc catalyst with fluorination chrome catalysts, the fluorination zinc catalyst is matched somebody with somebody with being fluorinated the quality of chrome catalysts
Than for 50~95:5~50.Preferably, the fluorination zinc catalyst and the quality proportioning for being fluorinated chrome catalysts are 70~90:10
~30.
Above-mentioned fluorination chrome catalysts, its specific surface area are 200~300m2/g.Preferably, the fluorination chrome catalysts
Specific surface area is 200~260m2/g。
Above-mentioned fluorination chrome catalysts, its pore volume are 0.4~0.7cm3.Preferably, the pore volume of the fluorination chrome catalysts
For 0.4~0.6cm3。
Above-mentioned fluorination chrome catalysts, its aperture areChoosing, the aperture of the fluorination chrome catalysts are
Present invention also offers the preparation method of the fluorination zinc catalyst, the preparation method includes：
The ether and/or alcoholic solution for making HF contact with organic zinc solution, the reaction product obtained after reaction through stand aging,
Remove organic solvent and obtain being fluorinated zinc catalyst after drying.
In the preparation method of fluorination zinc catalyst provided by the invention, HF ether and/or alcoholic solution are used.Both can make
With HF diethyl ether solution, HF alcoholic solution can also be used, or uses HF ether and alcoholic solution.
Wherein described alcohol, be preferably selected from one kind in methanol, ethanol and isopropanol, two or three.
Wherein described HF ether and/or the concentration of alcoholic solution meet to be smoothed out reaction.Preferably, it is described
HF ether and/or the concentration of alcoholic solution are 0.3~10mol/L, and more preferably 0.4~3mol/L.
In the preparation method of fluorination zinc catalyst provided by the invention, organic zinc solution contains zinc salt and organic molten
Agent.
Wherein described zinc salt is selected from zinc halide, zinc nitrate, zinc sulfate, C1-C4Fatty acid zinc salt and C1-C4Fatty alcohol zinc salt
At least one of.Preferably, the zinc salt be selected from zinc chloride, zinc nitrate, zinc formate, zinc acetate, zinc oxalate, zinc propionate,
One kind, two or three of combination of the above in ethanol zinc.It may further be preferable that the zinc salt is selected from zinc formate, zinc acetate, third
Sour zinc, methanol zinc and one kind, two or three of combination of the above in ethanol zinc.
Wherein described organic solvent is selected from C1-4Alcohol, C1-4Ester, C1-4Amine, benzene, C1-4One kind in alkyl-substituted benzene, two kinds
Or three kinds of combination of the above.Preferably, the organic solvent is selected from methanol, ethanol, propyl alcohol, butanol, amylalcohol, acetone, butanone, first
One in ether, ether, propyl ether, tetrahydrofuran, dioxane, dimethyl sulfoxide, dimethylformamide, benzene, toluene and dimethylbenzene
Kind, two or three of combination of the above.It may further be preferable that the organic solvent be selected from methanol, ethanol, propyl alcohol, butanol, benzene,
One kind, two or three of combination of the above in toluene and dimethylbenzene.
In wherein organic zinc solution, the molar concentration of zinc salt meets to be smoothed out reaction.Preferably, the zinc
The molar concentration of salt is 0.05~5mol/L, and more preferably 0.1~2.5mol/L.
In the preparation method of fluorination zinc catalyst provided by the invention, the molar ratio of HF and zinc salt meets to make reaction smooth
Progress.Preferably, the molar ratio of the HF and zinc salt are 1.0~3.0:1, and more preferably 1.5~2.0:
1。
The preparation method of fluorination zinc catalyst provided by the invention is not required particularly reaction temperature.To make reaction more
Smoothly carrying out, the reaction temperature is preferably -70~120 DEG C, and more preferably 0 DEG C~50 DEG C.
In the preparation method of fluorination zinc catalyst provided by the invention, the method for removing organic solvent, preferably it is
Selected from vacuum distillation, centrifugation, rotary evaporation or freezing separation.When using rotary evaporation violate the law remove organic solvent when, rotation
It is preferably 50~70 DEG C to turn evaporating temperature.
In the preparation method of fluorination zinc catalyst provided by the invention, the fluorination zinc catalyst of preparation preferably enters with pore creating material
Row is dry-mixed.When zinc catalyst will be fluorinated and pore creating material progress is dry-mixed, the quality proportioning of the fluorination zinc catalyst and pore creating material
Preferably 100:1~10, and more preferably 100:1~4.Preferably, the pore creating material is selected from polyethylene glycol, stearic acid
At least one of with laurate.
Fluorination chrome catalysts provided by the invention, it can obtain according to the preparation method of above-mentioned fluorination zinc catalyst, also may be used
To be obtained by buying pattern.
Catalyst provided by the invention, is suitable for exchange chloride for fluoride.Particularly suitable for the chloro- 2,2,2- trifluoros second of l-
The synthesis of alkane, 3,3,3- trifluoro propenes, 1,1,1,2,3- pentachloropropanes or 2,3,3,3- tetrafluoropropenes.Especially particularly suitable for
L- chloro-2,2,2-trifluoroethanes are synthesized by trichloro ethylene, 2,3,3,3- tetrafluoros third are prepared by the chloro- 3,3,3- trifluoro propenes fluorinations of 2-
Alkene, perfluoroethane is synthesized by a chloropentafluoroethane or 2,3,3,3- tetrafluoros third are prepared by 1,1,1,2,3- pentachloropropanes (R244bb)
Alkene.
Catalyst provided by the invention, when for exchange chloride for fluoride, there is higher conversion ratio compared with prior art
And selectivity, and there is cost advantage.
Embodiment
The present invention is further described with reference to specific embodiment, but does not limit the invention to these tools
Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope
All alternatives, improvement project and equivalents.
Embodiment 1
Take 39.54g Zn (CH3COO)2It is dissolved in 500ml methanol, stirs, forms zinc solution.At room temperature, will be dissolved with 10.0g
The HF-Et of anhydrous HF2O solution (12.5mol/L) adds above-mentioned zinc solution, is stirred vigorously, and reaction stops stirring after 4 hours, quiet
Put aging 4 hours.The volatile components in product are removed using Rotary Evaporators or centrifuge, are put into vacuum drying oven drying
Afterwards, high-specific surface area zinc fluoride is produced, is designated as ZnF2-1。
Embodiment 2
Take 51.08g Zn (MeO)2It is dissolved in 500ml methanol, stirs, forms zinc solution.At room temperature, will dissolved with 20.0g without
Water HF HF-Et2O solution (12.5mol/L) adds above-mentioned zinc solution, is stirred vigorously, and reaction stops stirring after 4 hours, stands
Aging 4 hours.The volatile components in product are removed using Rotary Evaporators or centrifuge, are put into vacuum drying oven drying
Afterwards, high-specific surface area zinc fluoride is produced, is designated as ZnF2-2。
Embodiment 3
Take 52.72g Zn (CH3COO)2It is dissolved in 500ml methanol, stirs, forms zinc solution.At room temperature, will be dissolved with 10.0g
The HF-Et of anhydrous HF2O solution (12.5mol/L) adds above-mentioned zinc solution, is stirred vigorously, and reaction stops stirring after 4 hours, quiet
Put aging 4 hours.The volatile components in product are removed using Rotary Evaporators or centrifuge, are put into vacuum drying oven drying
Afterwards, high-specific surface area zinc fluoride is produced, is designated as ZnF2-3。
Embodiment 4
Take 49.42g Zn (CH3COO)2It is dissolved in 500ml methanol, stirs, forms zinc solution.At room temperature, will be dissolved with 10.0g
The HF-Et of anhydrous HF2O solution (12.5mol/L) adds above-mentioned zinc solution, is stirred vigorously, and reaction stops stirring after 4 hours, quiet
Put aging 4 hours.The volatile components in product are removed using Rotary Evaporators or centrifuge, are put into vacuum drying oven drying
Afterwards, high-specific surface area zinc fluoride is produced, is designated as ZnF2-4。
Embodiment 5
Take 52.72g Zn (CH3COO)2It is dissolved in 500ml methanol, stirs, forms zinc solution., will be molten in the environment of 0 DEG C
There is the HF-Et of 12.0g anhydrous HFs2O solution (12.5mol/L) adds above-mentioned zinc solution, is stirred vigorously, and reaction stops after 4 hours
Stirring, stand aging 4 hours.The volatile components in product are removed using Rotary Evaporators or centrifuge, are put into vacuum
After oven drying, high-specific surface area zinc fluoride is produced, is designated as ZnF2-5。
Embodiment 6
Take 54.56g (C3H5O3)2Zn is dissolved in 500ml ethanol, stirring, forms zinc solution.At room temperature, will be dissolved with
The HF-Et of 10.0g anhydrous HFs2O solution (12.5mol/L) adds above-mentioned zinc solution, is stirred vigorously, and reaction stops stirring after 4 hours
Mix, stand aging 4 hours.The volatile components in product are removed using Rotary Evaporators or centrifuge, are put into vacuum baking
After case is dried, high-specific surface area zinc fluoride is produced, is designated as ZnF2-6。
Embodiment 7
Take 68.15g ZnCl2It is dissolved in 600ml ethanol, stirs, forms zinc solution.At room temperature, will dissolved with 10.0g without
Water HF HF-Et2O solution (12.5mol/L) adds above-mentioned zinc solution, is stirred vigorously, and reaction stops stirring after 4 hours, stands
Aging 4 hours.The volatile components in product are removed using Rotary Evaporators or centrifuge, are put into vacuum drying oven drying
Afterwards, it is designated as ZnF2-7。
Embodiment 8
Take 74.37g ZnNO3·6H2O is dissolved in 600ml ethanol, stirring, forms zinc solution.At room temperature, will be dissolved with
The HF-Et of 5.0g anhydrous HFs2O solution (12.5mol/L) adds above-mentioned zinc solution, is stirred vigorously, and reaction stops stirring after 4 hours
Mix, stand aging 4 hours.Reacted product is filtered by vacuum, and after filter cake is put into vacuum drying oven drying, is designated as ZnF2-
8。
It is as shown in table 1 by BET isothermal nitrogen adsorption assay specific surface areas, embodiment 1-8.
Fluorination zinc precursor specific surface area is prepared under table 1, different condition
The present invention has further investigated its effect in catalytic reaction after high-specific surface area zinc fluoride is obtained.
Embodiment 9：Chloro- 3,3,3- trifluoro propenes (HCFO-1233xf) fluorinations of 2- prepare 2,3,3,3- tetrafluoropropenes (HFO-
1234yf)
Fluorination chrome catalysts are mixed with fluorination zinc catalyst prepared by embodiment 2, add the tristearin of 1% mass fraction
Acid, catalyst is obtained after tabletting (5 × 5mm of φ).The fluorination chrome catalysts are 1.5 with the mass ratio for being fluorinated zinc catalyst:10,
And the specific surface area of the fluorination chrome catalysts is (202) m2/ g, pore volume are (0.47) cm3, aperture be
Obtained catalyst is loaded in nickel φ 19 × 2mm reaction tubes, loadings 50ml.Adjusting temperature of reactor is
370 DEG C, HCFC-1233xf (60ml/min), oxygen (10ml/min) and HF (600ml/min), reaction time 16h are passed through,
React and reaction product is removed into HCl and HF through washing, alkali cleaning after terminating, then formed with gas chromatographic analysis product, as a result seen
Table 2.
Table 2, the catalyst related activity data of embodiment 9
Embodiment 10：One chloropentafluoroethane (R115) synthesis perfluoroethane (R116)
Fluorination chrome catalysts are mixed with fluorination zinc catalyst prepared by embodiment 3, add the tristearin of 1% mass fraction
Acid, catalyst is obtained after tabletting (5 × 5mm of φ).The fluorination chrome catalysts are 1 with the mass ratio for being fluorinated zinc catalyst:9, and
The specific surface area of the fluorination chrome catalysts is (236) m2/ g, pore volume are (0.58) cm3, aperture be
Obtained catalyst is loaded in nickel φ 19 × 2mm reaction tubes, loadings 60ml.Adjusting temperature of reactor is
420 DEG C, it is passed through R115 (30ml/min) and HF (60ml/min), reaction time 22h.React reaction product after terminating through water
Wash, alkali cleaning removing HCl and HF, then formed with gas chromatographic analysis product, the results are shown in Table 3.
The catalyst related activity data of 3 embodiment of table 10
Embodiment 11：1,1,1,2,3- pentachloropropanes (R244bb) prepare 2,3,3,3- tetrafluoropropenes (R1234yf)
Fluorination chrome catalysts are mixed with fluorination zinc catalyst prepared by embodiment 4, add the tristearin of 1% mass fraction
Acid, catalyst is obtained after tabletting (5 × 5mm of φ).The fluorination chrome catalysts are 2 with the mass ratio for being fluorinated zinc catalyst:10, and
The specific surface area of the fluorination chrome catalysts is (288) m2/ g, pore volume are (0.67) cm3, aperture be
Obtained catalyst is loaded to the middle part of nickel alloy pipe (46 × 3mm of φ) fixed bed reactors, loadings 50ml.
Reacting furnace temperature is slowly increased to 400 DEG C, is passed through R244bb (20ml/min) and nitrogen (30ml/min).Reaction will reaction after terminating
Product removes HCl and HF through washing, alkali cleaning, is then formed with gas chromatographic analysis product, the results are shown in Table 4.
Table 4, the catalyst related activity data of embodiment 11
Embodiment 12：Trichloro ethylene (TCE) synthesis 1,1,1- trifluoro-2-chloroethanes (R133a)
Fluorination chrome catalysts are mixed with fluorination zinc catalyst prepared by embodiment 5, add the tristearin of 1% mass fraction
Acid, catalyst is obtained after tabletting (5 × 5mm of φ).The fluorination chrome catalysts are 8 with the mass ratio for being fluorinated zinc catalyst:92, and
The specific surface area of the fluorination chrome catalysts is (229) m2/ g, pore volume are (0.55) cm3, aperture be
Obtained catalyst is loaded to the middle part of nickel alloy pipe (46 × 3mm of φ) fixed bed reactors, loadings 50ml.
Reacting furnace temperature is slowly increased to 260 DEG C, is passed through TCE (45ml/min) and HF (360ml/min).React reaction product after terminating
HCl and HF is removed through washing, alkali cleaning, is then formed with gas chromatographic analysis product, the results are shown in Table 5.
Table 5, the catalyst related activity data of embodiment 12
Embodiment 13, trichloro ethylene (TCE) synthesis 1,1,1- trifluoro-2-chloroethanes (R133a)
By embodiment 5 prepare fluorination zinc catalyst add 1% mass fraction stearic acid, be well mixed tabletting (φ 5 ×
5mm) load the middle part of nickel alloy pipe (46 × 3mm of φ) fixed bed reactors, loadings 50ml afterwards.Reacting furnace temperature slowly rises
To 260 DEG C, TCE (45ml/min) and HF (360ml/min) are passed through.Reaction removes reaction product through washing, alkali cleaning after terminating
HCl and HF, then formed with gas chromatographic analysis product, the results are shown in Table 6.
Table 6, the catalyst related activity data of embodiment 13
Embodiment 14：One chloropentafluoroethane (R115) synthesis perfluoroethane (R116)
Fluorination zinc catalyst prepared by embodiment 3 is added to the stearic acid of 1% mass fraction, after tabletting (5 × 5mm of φ)
To catalyst.Obtained catalyst is loaded in nickel φ 19 × 2mm reaction tubes, loadings 60ml.Adjusting temperature of reactor is
420 DEG C, it is passed through R115 (30ml/min) and HF (60ml/min), reaction time 22h.React reaction product after terminating through water
Wash, alkali cleaning removing HCl and HF, then formed with gas chromatographic analysis product, the results are shown in Table 7.
The catalyst related activity data of 7 embodiment of table 14
Claims (14)
1. a kind of catalyst of high-specific surface area, for exchange chloride for fluoride, it is characterised in that the catalyst contains zinc fluoride
Catalyst, and the specific surface area for being fluorinated zinc catalyst is 80~180m2/ g, pore volume are 0.15~0.50cm3, aperture be
2. according to the catalyst of the high-specific surface area described in claim 1, it is characterised in that the ratio table of the fluorination zinc catalyst
Area is 120~180m2/ g, pore volume are 0.28~0.50cm3, aperture be
3. according to the catalyst of the high-specific surface area described in claim 2, it is characterised in that the ratio table of the fluorination zinc catalyst
Area is 140~180m2/ g, pore volume are 0.40~0.50cm3, aperture be
4. according to the catalyst of the high-specific surface area described in claim 1, it is characterised in that the catalyst further contains
Chrome catalysts are fluorinated, the fluorination zinc catalyst is 50~95 with the quality proportioning for being fluorinated chrome catalysts:5~50, charomic fluoride is urged
The specific surface area of agent is 200~300m2/ g, pore volume are 0.40~0.70cm3, aperture be
5. according to the catalyst of the high-specific surface area described in claim 4, it is characterised in that the fluorination zinc catalyst and fluorination
The quality proportioning of chrome catalysts is 70~90:10~30, the specific surface area of the fluorination chrome catalysts is 200~260m2/ g, hole
Hold for 0.4~0.6cm3, aperture be
6. according to the catalyst of the high-specific surface area described in claim 1, it is characterised in that the preparation of the fluorination zinc catalyst
Method includes：
The ether and/or alcoholic solution for making HF contact with organic zinc solution, and the reaction product obtained after reaction is through standing aging, removing
Obtain being fluorinated zinc catalyst after organic solvent and drying；
Organic zinc solution contains zinc salt and organic solvent；
The zinc salt is selected from zinc halide, zinc nitrate, zinc sulfate, C1-C4Fatty acid zinc salt and C1-C4At least one in fatty alcohol zinc salt
Kind；
The organic solvent is selected from C1-4Alcohol, C1-4Ester, C1-4Amine, benzene, C1-4One kind in alkyl-substituted benzene, two or three with
Upper combination.
7. according to the catalyst of the high-specific surface area described in claim 6, it is characterised in that：
In the ether and/or alcoholic solution of the HF：One kind in methanol, ethanol and isopropanol of the alcohol, two or three；
One kind in zinc chloride, zinc nitrate, zinc formate, zinc acetate, zinc oxalate, zinc propionate, ethanol zinc of the zinc salt, two kinds
Or three kinds of combination of the above；
The organic solvent is selected from methanol, ethanol, propyl alcohol, butanol, amylalcohol, acetone, butanone, methyl ether, ether, propyl ether, tetrahydrochysene
One kind, more than two or three group in furans, dioxane, dimethyl sulfoxide, dimethylformamide, benzene, toluene and dimethylbenzene
Close；
The ether of the HF and/or the concentration of alcoholic solution are 0.3~10mol/L；
The molar ratio of HF and zinc salt is 1.0~3.0:1；
In organic zinc solution, the molar concentration of zinc salt is 0.05~5mol/L；
Reaction temperature is -70~120 DEG C.
8. according to the catalyst of the high-specific surface area described in claim 7, it is characterised in that：
One kind, more than two or three group of the zinc salt in zinc formate, zinc acetate, zinc propionate, methanol zinc and ethanol zinc
Close；
One kind in methanol, ethanol, propyl alcohol, butanol, benzene, toluene and dimethylbenzene of the organic solvent, two or three with
Upper combination；
The ether and/or alcoholic solution concentration of the HF is 0.4~3mol/L；
The mol ratio of the HF and zinc salt are 1.5~2.0:1；
In organic zinc solution, the molar concentration of zinc salt is 0.1~2.5mol/L；
The reaction temperature is 0 DEG C~50 DEG C.
9. according to the catalyst of the high-specific surface area described in claim 6, it is characterised in that the method for removing organic solvent
Selected from vacuum distillation, centrifugation, rotary evaporation or freezing separation.
10. according to the catalyst of the high-specific surface area described in claim 9, it is characterised in that the method for removing organic solvent
For rotary evaporation, rotating evaporation temperature is 50~70 DEG C.
11. according to the catalyst of the high-specific surface area described in claim 6, it is characterised in that make fluorination zinc catalyst and pore creating material
Carry out it is dry-mixed, it is described fluorination zinc catalyst and pore creating material quality proportioning be 100:1~10.
12. according to the catalyst of the high-specific surface area described in claim 11, it is characterised in that the pore creating material is selected from poly- second two
At least one of alcohol, stearic acid and laurate, the quality proportioning of the fluorination zinc catalyst and pore creating material is 100:1~4.
13. according to the catalyst of the high-specific surface area described in one of claim 1 to 5, it is characterised in that the catalyst is used for
The conjunction of l- chloro-2,2,2-trifluoroethanes, 3,3,3- trifluoro propenes, 1,1,1,2,3- pentachloropropanes or 2,3,3,3- tetrafluoropropenes
Into.
14. according to the catalyst of the high-specific surface area described in claim 13, it is characterised in that the catalyst is used for by trichlorine
Ethylene synthase l- chloro-2,2,2-trifluoroethanes, prepared by the fluorination of 2- chloro- 3,3,3- trifluoro propenes 2,3,3,3- tetrafluoropropenes, by
One chloropentafluoroethane synthesizes perfluoroethane or prepares 2,3,3,3- tetrafluoropropenes by 1,1,1,2,3- pentachloropropanes (R244bb).
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| CN114515583A (en) * | 2020-11-20 | 2022-05-20 | 浙江省化工研究院有限公司 | Preparation method and application of chromium fluoride-doped sulfate catalyst |
| CN114515583B (en) * | 2020-11-20 | 2023-12-19 | 浙江省化工研究院有限公司 | Preparation method and application of fluorine-chromium doped sulfate catalyst |
| CN113075148A (en) * | 2021-03-22 | 2021-07-06 | 久泰能源(准格尔)有限公司 | Method for measuring carbon content on surface of catalyst in MTO (methanol to olefin) process |
| 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 |
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