CN101264450A - Preparation of full microwave radiation method sulfur-tolerant type molybdenum base catalyst - Google Patents

Preparation of full microwave radiation method sulfur-tolerant type molybdenum base catalyst Download PDF

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CN101264450A
CN101264450A CNA200810025413XA CN200810025413A CN101264450A CN 101264450 A CN101264450 A CN 101264450A CN A200810025413X A CNA200810025413X A CN A200810025413XA CN 200810025413 A CN200810025413 A CN 200810025413A CN 101264450 A CN101264450 A CN 101264450A
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catalyst
microwave
preparation
microwave radiation
microwave reactor
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CN100569366C (en
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魏贤勇
宗志敏
周肖
赵建军
马玉苗
谢瑞伦
魏艳彬
李建军
彭耀丽
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China University of Mining and Technology CUMT
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a preparation method of total microwave-assisted sulfur-tolerant molybdenum based catalyst, belonging to the technical field of preparation methods of molybdenum-based catalyst. The preparation method comprises the following steps: (1) AlCl3 and NaOH with molar ratio 1:1 are mixed together to make Al (OH) 3, the Al (OH) 3 is deposited in the microwave reactor to bake, and the Al2O3 catalyst carrier is acquired, (2) Al2O3 and saturated potassium carbonate aqueous solution are added into the microwave reactor, microwave-heated and stirred, the pumping filtration of solution is processed, filter cake is added into the microwave reactor and microwave-heated in the nitrogen airflow, and K/Al2O3 catalyst carrier is acquired, (3) K/Al2O3 and saturated (NH4)2MoS4 solution are added into the microwave reactor, microwave-heated and stirred, the pumping filtration of solution is processed, filter cake is added into microwave reactor and microwave-heated in the nitrogen airflow, and the active ingredient of K-MoS2/Al2O3 catalyst is prepared, and (4) the active ingredient of K-MoS2/Al2O3 catalyst is adopted as the main material, the processes of (2) and (3) are repeated for 1-4 times. The total microwave-assisted slurry bed sulfur-tolerant vulcanization molybdenum based catalyst has the advantages of high transformation performance and efficiency of CO, good selectivity of transformation product, sulfur-tolerant and resistance to carbon deposition performance, mild reaction conditions, low energy consumption, short preparation time, and simple technology.

Description

The preparation method of full microwave radiation sulfur-tolerant type molybdenum base catalyst
Technical field
The present invention relates to a kind of preparation method of catalyst with base of molybdenum, particularly a kind of preparation method of full microwave radiation sulfur-tolerant type molybdenum base catalyst.
Background technology
The sulfur-tolerant type catalyst of research is mainly catalyst with base of molybdenum at present, and it comprises that mainly the oxidation state catalyst with base of molybdenum is (as KCl-MoO 3/ ZrO 2) and the sulphided state catalyst with base of molybdenum (as Ni-K 2CO 3-MoS 2/ SiO 2) two major types.The sulphided state catalyst with base of molybdenum extensively is subjected to people's attention owing to have higher activity, and its main preparation methods comprises:
(1) conventional thermal decomposition preparation method: 2mol/L (NH 4) 6Mo 7O 244H 2(the NH of the same concentrations of O aqueous solution 15mL and 5 times of volumes 4) 2The S aqueous solution stirred one hour at 60 ℃, and 60-70 ℃ of lower vacuum drying makes (NH 4) 2MoS 4Behind the solid, at 500 ℃ of N 2Add thermal decomposition under the protection and obtain MoS 2, again with 0.2 times of (NH 4) 2MoS 4The K of amount of solid 2CO 3The pressed powder mixing gets final product.
(2) coprecipitation: with the nickel molybdenum than the 1mol/L nickel nitrate and the 2mol/L (NH that are 0.5 times 4) 2Mo 4The aqueous solution splashes in 60 ℃ 30% the acetic acid aqueous solution jointly, stirs behind the 1h the mixture cool to room temperature that obtains, aging, filtration, drying.Sneak into then 0.2 times of (NH 4) 2MoS 4The K of amount of solid 2CO 3Pressed powder is at N 2The lower heating 1h of protection.
(3) sol-gel process: the mol ratio in molybdenum and cobalt is that 1: 1 ratio is with (NH 4) 6Mo 7O 246H 2O and required cobalt nitrate are made the 500ml aqueous solution, add the citric acid of 1-5ml again.PH neutral value with ammoniacal liquor or formic acid regulator solution.Place water-bath heating, aging back solution to change into gel solution.With colloidal sol 120 ℃ of dryings, roasting 4h under selected temperature then.At last with the CS of hydrogen by 0 ℃ 2Can obtain corresponding sulphided state sample as sulfiding gas sulfidation-oxidation aspect product.
People utilize microwave radiation, heating principle once to explore the work of the impregnating aspect of the modification of carrier in the catalyst preparation process and load composition:
(1) MgO solid-carrying type list bimetallic alloy catalyst, its method are the MgO solid to be immersed contain in single bimetal salt solution, and the catalyst precursor that takes out load is placed on heat treated in the microwave field;
(2) utilize the hydrothermal synthesis method that changes pH condition and hot water boiling carrier, the molecular sieve presoma of the different Si/Al ratios that obtain heats in microwave again, can Rapid Modification SiO 2, Al 2O 3Original skeleton structure in the carrier, and preparation A, X and Y zeolite and ZSM-5 catalyst;
(3) under the carry out microwave radiation heating condition, utilize the method in microwave, flood can be on molecular sieve carrier or template load C o/NaX or the slaines such as Co, Ni, can prepare multiple catalysis material.
Complex technical process, the efficient of above-mentioned preparation sulfur-tolerant type catalyst are low.
Summary of the invention
The objective of the invention is to provide a kind of: the preparation method of the full microwave radiation sulfur-tolerant type molybdenum base catalyst that technical process is simple, efficient is high
The object of the present invention is achieved like this:
(1) with the AlCl of equimolar ratio example 3Fully mix with the NaOH powder, prepare Al (OH) 3, again with fresh Al (OH) 3100 gram solids are positioned in the microwave reactor of 500W-800W power, and the temperature that keeps carry out microwave radiation heating under the protection of nitrogen stream is at 450 ℃-500 ℃, and roasting 30 minutes-120 minutes obtains Al 2O 3Catalyst carrier;
(2) in microwave reactor, add 1: 1-1: the Al of 5 mol ratios 2O 3Amount of solid and 1mol/L unsaturated carbonate aqueous solutions of potassium; the temperature of carry out microwave radiation heating remains in 100 ℃ of-140 ℃ of scopes; continuous stirring is suction filtration solution after 0.5 hour; be reentered in the microwave reactor after scattered the filter cake that obtains; the temperature of carry out microwave radiation heating remains in 450 ℃ of-500 ℃ of scopes under the stream of nitrogen gas protection, has prepared the K/Al of load potassium after the roasting 2O 3Catalyst carrier;
(3) in microwave reactor, add 1: 1-1: the K/Al of 5 mol ratios 2O 3Saturated (the NH of amount of solid and 1mol/L 4) 2MoS 4Solution, the temperature of carry out microwave radiation heating remains in 200 ℃ of-240 ℃ of scopes, continuous stirring is suction filtration solution after 0.5 hour, again be reentered in the microwave reactor after scattered the filter cake that obtains, the temperature of carry out microwave radiation heating keeps being arranged in 400 ℃ of-500 ℃ of scopes under the stream of nitrogen gas condition, and roasting has prepared K-MoS after 30 minutes-120 minutes 2/ Al 2O 3Catalyst active ingredient;
(4) with K-MoS 2/ Al 2O 3Catalyst active ingredient is raw material, according to step (2) and (3) repeatable operation 1-4 time, has finished slurry attitude bed sulfur-tolerant type catalyst K-MoS 2/ Al 2O 3Preparation.
Beneficial effect: owing to adopted such scheme, adopt heating using microwave effectively to shorten the time of Kaolinite Preparation of Catalyst, improve the crystal type of catalyst surface, make the carrier A l2O of slurry attitude bed sulfur-tolerant type molybdenum sulphide based 3Crystal grain is more evenly tiny and fine and close, and specific area is big, crystallization velocity is fast, even aperture distribution and regular, good thermal stability; Improve the activity of catalyst, the crystalline form particle that promotes slurry attitude bed sulfur-tolerant type molybdenum sulphide based evenly, sharpness of border and compound with regular structure, effectively stoped the reunion effect between the catalyst particle of load crystal; Employing microwave dipping, impel in the slurry attitude bed sulfur-tolerant type catalyst the pay(useful) load element evenly, high degree of dispersion on the surfaces externally and internally of carrier, greatly improved the effective load effect of catalyst, technical process is simple, the efficient height has reached purpose of the present invention.
Advantage: the slurry attitude bed sulfur-tolerant type molybdenum sulfide base catalysis fixture of full heating using microwave preparation has higher CO changing effect, the transformation efficiency height, converted product has good selectivity, have tangible anti-sulphur effect and anti-carbon deposit performance simultaneously, effectively improved the process conditions of Preparation of Catalyst, it is simple that full microwave heating method prepares sulfur-tolerant type catalyst reaction mild condition, little, the consuming time weak point of energy consumption, technology.
The specific embodiment
Embodiment 1:
Slurry attitude bed sulfur-tolerant type catalyst K-MoS under full microwave condition 2/ Al 2O 3Performance indications and the catalytic effect of preparation method, operating condition and catalyst:
1, Preparation of catalysts:
(1) takes by weighing the freshly prepd Al of 100g (OH) 3And be positioned in the microwave reactor of 500W power, remain on 450 ℃ of roastings in the temperature of carry out microwave radiation heating under the nitrogen protection condition and prepared catalyst carrier (Al after 100 minutes 2O 3).
(2) in microwave reactor, add Al 2O 32 times supersaturation solution of potassium carbonate of amount of solid; continuous stirring suction filtration solution after 0.5 hour when the temperature of carry out microwave radiation heating remains on 100 ℃; be reentered in the microwave reactor after scattered the filter cake that obtains, roasting had prepared the catalyst carrier (K/Al of load potassium when the temperature of carry out microwave radiation heating remained on 450 ℃ under the stream of nitrogen gas protection after 50 minutes 2O 3).
(3) in microwave reactor, add K/Al 2O 34 times supersaturation (NH of amount of solid 4) 2MoS 4Solution, continuous stirring suction filtration solution after 0.5 hour when the temperature of carry out microwave radiation heating remains on 240 ℃, again be reentered in the microwave reactor after scattered the filter cake that obtains, roasting prepared K-MoS after 100 minutes when the temperature of carry out microwave radiation heating kept being arranged on 400 ℃ under the stream of nitrogen gas condition 2/ Al 2O 3Catalyst active ingredient.
(4) with K-MoS 2/ Al 2O 3Catalyst active ingredient is raw material, again operates 3 times according to method and the step of (2) and (3), has finished slurry attitude bed sulfur-tolerant type catalyst K-MoS 2/ Al 2O 3Preparation.
2, the performance indications of catalyst and catalytic effect:
Slurry attitude bed sulfur-tolerant type catalyst K-MoS 2/ Al 2O 3The mass content of middle effective element is respectively: K 1.85%, S1.56%, Mo 1.20%, wherein catalyst active ingredient is with MoS 2Be main; Specific area is 160.1m 2/ g, total pore volume is 241.4cc/g, average pore size is
Figure A20081002541300051
In paste state bed reactor, with H 2: CO: Ar=73.5: when 24: 2.5 artificial synthetic reformed gas was raw material, initial pressure was 3MPa, kept reaction temperature to stir 5h in 240 ℃ of-260 ℃ of scopes, and the conversion ratio of CO is 58%.Main effectively product comprises methyl alcohol, ethanol, higher alcohols, a spot of lower carbon number hydrocarbons, and wherein the selectivity of methyl alcohol and ethanol one way is respectively 1.38%, 0.75%, and the selectivity of higher alcohol and hydrocarbon product one way is about 91.62%.Compare the K-MoS of this method preparation by the catalyst with conventional method thermal decomposition acquisition 2/ Al 2O 3Catalyst has higher anti-sulphur and anti-carbon deposit effect.
Embodiment 2:
1, Preparation of catalysts:
(1) takes by weighing the freshly prepd Al of 100g (OH) 3And be positioned in the microwave reactor of 600w power, the temperature of carry out microwave radiation heating remains in 500 ℃ of scopes under the nitrogen protection condition, and roasting has prepared catalyst A l after 80 minutes 2O 3Carrier.
(2) in microwave reactor, add the Al of 1: 4 mol ratio 2O 3Amount of solid and 1mol/L unsaturated carbonate aqueous solutions of potassium; continuous stirring suction filtration solution after 0.5 hour when the temperature of carry out microwave radiation heating remains on 120 ℃; be reentered in the microwave reactor after scattered the filter cake that obtains, the temperature of carry out microwave radiation heating remains on 500 ℃ of roasting roastings have prepared load potassium after 120 minutes K/Al under the stream of nitrogen gas protection 2O 3Catalyst carrier.
(3) in microwave reactor, add the K/Al of 1: 5 mol ratio 2O 3Amount of solid and the 1mol/L (NH that satisfies 4) 2MoS 4Solution, continuous stirring suction filtration solution after 0.5 hour when the temperature of carry out microwave radiation heating remains on 220 ℃, again be reentered in the microwave reactor after scattered the filter cake that obtains, roasting prepared K-MoS after 120 minutes when the temperature of carry out microwave radiation heating kept being arranged on 450 ℃ under the stream of nitrogen gas condition 2/ Al 2O 3Catalyst active ingredient.
(4) with K-MoS 2/ Al 2O 3Catalyst active ingredient is raw material, according to the method for (2) and (3) and step repeatable operation 2 times, has finished slurry attitude bed sulfur-tolerant type catalyst K-MoS 2/ Al 2O 3Preparation.
2, the performance indications of catalyst and catalytic effect:
Slurry attitude bed sulfur-tolerant type catalyst K-MoS 2/ Al 2O 3The mass content of middle effective element is respectively: K 1.65%, S1.72%, Mo 1.80%, wherein catalyst active ingredient is with MoS 2Be main; Specific area is 166.0m 2/ g, total pore volume is 238.2cc/g, average pore size is
Figure A20081002541300052
In paste state bed reactor, with H 2: CO: Ar=73.5: when 24: 2.5 artificial synthetic reformed gas was raw material, initial pressure was 3MPa, kept reaction temperature to stir 5h in 240 ℃ of-260 ℃ of scopes, and the conversion ratio of CO is 64%.Main effectively product comprises methyl alcohol, ethanol, higher alcohols, a spot of lower carbon number hydrocarbons, and wherein the selectivity of alcohol product one way is respectively 1.42%, 1.22%, and the selectivity of higher alcohol and hydrocarbon product one way is about 90.44%.Compare the K-MoS of this method preparation by the catalyst with conventional method thermal decomposition acquisition 2/ Al 2O 3Catalyst has higher anti-sulphur and anti-carbon deposit effect.
Embodiment 3:
1, Preparation of catalysts:
(1) takes by weighing the AlCl that utilizes the equimolar ratio example 3With the prepared fresh Al (OH) of NaOH 3The 100g solid also is positioned in the microwave reactor of 800W power, and roasting obtained Al after 120 minutes when the temperature of maintenance carry out microwave radiation heating was at 400 ℃ under nitrogen stream is protected 2O 3Catalyst carrier.
(2) in microwave reactor, add Al 2O 35 times supersaturation solution of potassium carbonate of amount of solid; continuous stirring suction filtration solution after 0.5 hour when the temperature of carry out microwave radiation heating remains on 140 ℃; be reentered in the microwave reactor after scattered the filter cake that obtains, roasting had prepared the catalyst carrier (K/Al of load potassium when the temperature of carry out microwave radiation heating remained on 400 ℃ under the stream of nitrogen gas protection after 80 minutes 2O 3).
(3) in microwave reactor, add K/Al 2O 32 times supersaturation (NH of amount of solid 4) 2MoS 4Solution, continuous stirring suction filtration solution after 0.5 hour when the temperature of carry out microwave radiation heating remains on 240 ℃, again be reentered in the microwave reactor after scattered the filter cake that obtains, roasting prepared K-MoS after 80 minutes when the temperature of carry out microwave radiation heating kept being arranged on 500 ℃ under the stream of nitrogen gas condition 2/ Al 2O 3Catalyst active ingredient.
(4) with K-MoS 2/ Al 2O 3Catalyst active ingredient is raw material, according to the method for (2) and (3) and step repeatable operation 1 time, has finished slurry attitude bed sulfur-tolerant type catalyst K-MoS 2/ Al 2O 3Preparation.
2, the performance indications of catalyst and catalytic effect:
Slurry attitude bed sulfur-tolerant type catalyst K-MoS 2/ Al 2O 3The mass content of middle effective element is respectively: K 1.95%, S1.49%, Mo 2.0%, wherein catalyst active ingredient is with MoS 2Be main; Specific area is 172.3m 2/ g, total pore volume is 245.6cc/g, average pore size is
Figure A20081002541300061
In paste state bed reactor, with H 2: CO: Ar=73.5: when 24: 2.5 artificial synthetic reformed gas was raw material, initial pressure was 3MPa, kept reaction temperature to stir 5h in 240 ℃ of-260 ℃ of scopes, and the conversion ratio of CO is 66%.Main effectively product comprises methyl alcohol, ethanol, higher alcohols, a spot of lower carbon number hydrocarbons, and wherein the selectivity of alcohol product one way is respectively 1.97%, 2.15%, and the selectivity of higher alcohol and hydrocarbon product one way is about 88.54%.Compare the K-MoS of this method preparation by the catalyst with conventional method thermal decomposition acquisition 2/ Al 2O 3Catalyst has higher anti-sulphur and anti-carbon deposit effect.

Claims (1)

1, a kind of preparation method of full microwave radiation method sulfur-tolerant type molybdenum base is characterized in that: (1) is with the AlCl of equimolar ratio example 3Fully mix with the NaOH powder, prepare Al (OH) 3, again with fresh Al (OH) 3100 gram solids are positioned in the microwave reactor of 500W-800W power, and the temperature that keeps carry out microwave radiation heating under the protection of nitrogen stream is at 450 ℃-500 ℃, and roasting 30 minutes-120 minutes obtains Al 2O 3Catalyst carrier;
(2) in microwave reactor, add 1: 1-1: the Al of 5 mol ratios 2O 3Amount of solid and 1mol/L unsaturated carbonate aqueous solutions of potassium; the temperature of carry out microwave radiation heating remains in 100 ℃ of-140 ℃ of scopes; continuous stirring is suction filtration solution after 0.5 hour; be reentered in the microwave reactor after scattered the filter cake that obtains; the temperature of carry out microwave radiation heating remains in 450 ℃ of-500 ℃ of scopes under the stream of nitrogen gas protection, has prepared the K/Al of load potassium after the roasting 2O 3Catalyst carrier;
(3) in microwave reactor, add 1: 1-1: the K/Al of 5 mol ratios 2O 3Saturated (the NH of amount of solid and 1mol/L 4) 2MoS 4Solution, the temperature of carry out microwave radiation heating remains in 200 ℃ of-240 ℃ of scopes, continuous stirring is suction filtration solution after 0.5 hour, again be reentered in the microwave reactor after scattered the filter cake that obtains, the temperature of carry out microwave radiation heating keeps being arranged in 400 ℃ of-500 ℃ of scopes under the stream of nitrogen gas condition, and roasting has prepared K-MoS after 30 minutes-120 minutes 2/ Al 2O 3Catalyst active ingredient;
(4) with K-MoS 2/ Al 2O 3Catalyst active ingredient is raw material, according to step (2) and (3) repeatable operation 1-4 time, has finished slurry attitude bed sulfur-tolerant type catalyst K-MoS 2/ Al 2O 3Preparation.
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Cited By (4)

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CN102614926A (en) * 2012-03-12 2012-08-01 中国矿业大学 Method for preparing loaded solid super acidic catalyst directly by microwave method
CN103693693A (en) * 2013-12-26 2014-04-02 湛江师范学院 Preparation method for synthesizing molybdenum sulfide nanospheres by microwave-assisted liquid phase deposition
CN111203229A (en) * 2020-02-19 2020-05-29 中国科学院过程工程研究所 Preparation method and application of supported composite oxide catalyst
WO2021223559A1 (en) * 2020-05-06 2021-11-11 江苏龙净科杰环保技术有限公司 Sulfur-resistant and water-resistant manganese-based low-temperature denitration catalyst and preparation method therefor

Family Cites Families (4)

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Publication number Priority date Publication date Assignee Title
JP2004344754A (en) * 2003-05-21 2004-12-09 National Institute Of Advanced Industrial & Technology Method for preparing catalyst composition for hydrogenating hydrocarbon
CN1286566C (en) * 2003-06-30 2006-11-29 中国石油化工股份有限公司 Hydrofining catalyst containing molybdenum and/or tungsten and nickel and/or cobalt and its preparation process
JP4482653B2 (en) * 2004-05-19 2010-06-16 独立行政法人産業技術総合研究所 Hydrocracking catalyst for catalytic cracking gasoline
CN1583273A (en) * 2004-06-11 2005-02-23 中山大学 Preparing method for loaded metal oxide catalyst

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102614926A (en) * 2012-03-12 2012-08-01 中国矿业大学 Method for preparing loaded solid super acidic catalyst directly by microwave method
CN102614926B (en) * 2012-03-12 2016-04-20 中国矿业大学 A kind of microwave method directly prepares the method for supported solid superacid acid catalyst
CN103693693A (en) * 2013-12-26 2014-04-02 湛江师范学院 Preparation method for synthesizing molybdenum sulfide nanospheres by microwave-assisted liquid phase deposition
CN111203229A (en) * 2020-02-19 2020-05-29 中国科学院过程工程研究所 Preparation method and application of supported composite oxide catalyst
WO2021223559A1 (en) * 2020-05-06 2021-11-11 江苏龙净科杰环保技术有限公司 Sulfur-resistant and water-resistant manganese-based low-temperature denitration catalyst and preparation method therefor

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