CN102921427A - Method for preparing gasoline hydrodesulfurization catalyst - Google Patents
Method for preparing gasoline hydrodesulfurization catalyst Download PDFInfo
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- CN102921427A CN102921427A CN 201210422141 CN201210422141A CN102921427A CN 102921427 A CN102921427 A CN 102921427A CN 201210422141 CN201210422141 CN 201210422141 CN 201210422141 A CN201210422141 A CN 201210422141A CN 102921427 A CN102921427 A CN 102921427A
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Abstract
The invention relates to a method for preparing a gasoline hydrodesulfurization catalyst, and belongs to the field of processing of gasoline additives. The method for preparing the gasoline hydrodesulfurization catalyst is characterized by comprising the following steps of: (1) preparing a magnalium composite oxide carrier: melting a certain amount of magnesium nitrate and aluminum nitrate into ionized water to obtain a solution, adjusting the pH value of the solution to be 9 to 10 by a using pH adjustment agent under certain hydrolysis temperature and a stirring state, reacting at constant temperature to obtain white pasty sedimentations, refluxing and crystallizing under certain crystallization temperature, drying the crystallized sedimentations at the temperature of 120 DEG C for 10 hours, and baking a dried product at certain baking temperature to obtain the magnalium composite oxide carrier; and (2) preparing the catalyst: mixing and immersing a maceration extract and the carrier for 4 hours by taking the mixed solution of the cobalt nitrate and ammonium molybdate which have the same volume as the maceration extract, drying at the temperature of 120 DEG C for 5 hours, baking at the temperature of 500 DEG C for 3 hours, grinding, so as to obtain particles of which the particle size is 3.0 to 4.0mm, so that the gasoline hydrodesulfurization catalyst is obtained. The gasoline hydrodesulfurization catalyst prepared by using the method has the characteristics of stable physicochemical property, high specific area, pore volume and relatively high desulfurization selectivity; and aw materials are readily available and are easy to process.
Description
Technical field
The present invention relates to a kind of preparation method of gasoline hydrodesulfurizationmethod catalyst, belong to the oil dope manufacture field.
Background technology
Sulphur in the gasoline and alkene can bring the discharging of harmful substance in the tail gas, so both at home and abroad having done a large amount of research work aspect reduction gasoline sulfur mass fraction and the olefin content, also have made some progress.For the higher characteristics of sulphur and olefin content in the Chinese catalytically cracked gasoline, develop the Hydrobon catalyst with good selectivity and have important practical significance.Wherein, catalyst carrier material to choose with preparing be the basis of this research work.Carried out a large amount of work around the catalyst for selectively hydrodesulfurizing take aluminium oxide as carrier both at home and abroad.
In the absorption of catalyst surface and the understanding of reaction property difference, the Acidity of Aikalinity of modulation carrier is to improve optionally one of effective ways of catalyst desulfurizing based on catalytic gasoline hydrogenation Sulfur During Process compound and alkene.Hydrotalcite-based compound (Mg-Al composite oxide) is the new catalytic material of quite being favored in recent years, it has cation interchangeability, acidity is adjustable and the duct is controlled characteristics, and the catalyst take it as carrier has advantages of the active component of making Mo, Co high degree of dispersion.These characteristics make hydrotalcite have as well behaved catalyst for selectively hydrodesulfurizing carrier may.The reports such as Bodily, the performance of the Hydrobon catalyst of preparation is better than with traditional A1 take hydrotalcite-based compound as predecessor
2O
3Catalyst for carrier.But how to improve the desulfuration selectivity of catalyst and the physicochemical properties of this type of catalysis material, and catalyst performance affect rule, also need go deep into and comprehensively study.
Therefore, study the preparation method of the catalyst of a kind of carrier for the gasoline hydrodesulfurizationmethod catalyst (Mg-Al composite oxide), make that its prepared Hydrobon catalyst has that physicochemical property is stable, the characteristics of high-specific surface area, pore volume and higher desulfuration selectivity, have certain economic benefit and social benefit.
Summary of the invention
The present invention aims to provide a kind of preparation method for the gasoline hydrodesulfurizationmethod catalyst, its prepared gasoline hydrodesulfurizationmethod catalyst has that physicochemical property is stable, the characteristics of high-specific surface area, pore volume and higher desulfuration selectivity, and raw material is easy to get, processes simple.
A kind of preparation method for the gasoline hydrodesulfurizationmethod catalyst of the present invention comprises.
(1) preparation of Mg-Al composite oxide carrier: a certain amount of magnesium nitrate and aluminum nitrate are dissolved in ionized water, under certain hydrolysis temperature and stirring, with the pH value conditioning agent pH value of solution is adjusted in PH9-10, under constant temperature, obtain white pasty state precipitation behind the hydrolysis, then crystallization refluxes under certain crystallization temperature, precipitation after the crystallization is 120 ℃ of lower dry 10 h after washing, and dried product is namely being obtained the Mg-Al composite oxide carrier after the roasting under certain sintering temperature.
(2) preparation of catalyst: take the mixed solution of isopyknic cobalt nitrate and ammonium molybdate as maceration extract, at room temperature with maceration extract and carrier hybrid infusion 4 h, 120 ℃ of drying 5 h, again in 500 ℃ of roasting 3 h, through getting the particle of particle diameter 3.0mm～4.0 mm after grinding, namely get gasoline hydrodesulfurizationmethod catalyst of the present invention.
Preferably, the hydrolysis temperature described in the step (1) is 70-90 ℃, and crystallization temperature is 60-80 ℃, and sintering temperature is 500-600 ℃.
Preferred, the pH value conditioning agent described in the step (1) is NaOH, potassium hydroxide, ammonia spirit.
Further preferably, the mass ratio of magnesium nitrate and aluminum nitrate is 8-12:1 described in the step (1).The amount ratio of maceration extract and carrier is 2-4:1 described in the step (2).
Still more preferably, the hydrolysis temperature described in the step (1) is 80 ℃, and crystallization temperature is 70 ℃, sintering temperature is 550 ℃, the pH value conditioning agent is ammonia spirit, and the mass ratio of magnesium nitrate and aluminum nitrate is 10:1, and the amount ratio of maceration extract and carrier is 3:1 described in the step (2).
The prepared gasoline hydrodesulfurizationmethod catalyst of the present invention has that physicochemical property is stable, the characteristics of high-specific surface area, pore volume and higher desulfuration selectivity, and raw material is easy to get, processes simple.
The specific embodiment
Embodiment one.
(1) preparation of Mg-Al composite oxide carrier: get the 100g magnesium nitrate and the 10g aluminum nitrate is dissolved in ionized water, under 80 ℃ and stirring, with pH value conditioning agent ammonia spirit the pH value of solution is adjusted in PH8.5, under constant temperature, obtain white pasty state precipitation behind the hydrolysis, then in certain 70 ℃ of lower backflow crystallization, precipitation after the crystallization is 120 ℃ of lower dry 10 h after washing, and dried product is namely obtained 71g Mg-Al composite oxide carrier after 550 ℃ of lower roastings.
(2) preparation of catalyst: the mixed solution of getting isopyknic cobalt nitrate and ammonium molybdate is maceration extract 300mL and Mg-Al composite oxide carrier 10g, at room temperature with maceration extract and carrier hybrid infusion 4 h, 120 ℃ of drying 5 h, again in 500 ℃ of roasting 3 h, through getting the particle of particle diameter 3.0mm～4.0 mm after grinding, namely get gasoline hydrodesulfurizationmethod catalyst 11g of the present invention.
Embodiment two.
(1) preparation of Mg-Al composite oxide carrier: get the 80g magnesium nitrate and the 10g aluminum nitrate is dissolved in ionized water, under 70 ℃ and stirring, with pH value conditioning agent ammonia spirit the pH value of solution is adjusted in PH8, under constant temperature, obtain white pasty state precipitation behind the hydrolysis, then in certain 60 ℃ of lower backflow crystallization, precipitation after the crystallization is 120 ℃ of lower dry 10 h after washing, and dried product is namely obtained 57g Mg-Al composite oxide carrier after 500 ℃ of lower roastings.
(2) preparation of catalyst: the mixed solution of getting isopyknic cobalt nitrate and ammonium molybdate is maceration extract 200mL and Mg-Al composite oxide carrier 10g, at room temperature with maceration extract and carrier hybrid infusion 4 h, 120 ℃ of drying 5 h, again in 500 ℃ of roasting 3 h, through getting the particle of particle diameter 3.0mm～4.0 mm after grinding, namely get gasoline hydrodesulfurizationmethod catalyst 10.3g of the present invention.
Embodiment three.
(1) preparation of Mg-Al composite oxide carrier: get the 120g magnesium nitrate and the 10g aluminum nitrate is dissolved in ionized water, under 90 ℃ and stirring, with pH value conditioning agent ammonia spirit the pH value of solution is adjusted in PH9, under constant temperature, obtain white pasty state precipitation behind the hydrolysis, then in certain 80 ℃ of lower backflow crystallization, precipitation after the crystallization is 120 ℃ of lower dry 10 h after washing, and dried product is namely obtained 62g Mg-Al composite oxide carrier after 600 ℃ of lower roastings.
(2) preparation of catalyst: the mixed solution of getting isopyknic cobalt nitrate and ammonium molybdate is maceration extract 400mL and Mg-Al composite oxide carrier 10g, at room temperature with maceration extract and carrier hybrid infusion 4 h, 120 ℃ of drying 5 h, again in 500 ℃ of roasting 3 h, through getting the particle of particle diameter 3.0mm～4.0 mm after grinding, namely get gasoline hydrodesulfurizationmethod catalyst 10.7g of the present invention.
Embodiment four.
The catalytic effect of gasoline hydrodesulfurizationmethod catalyst is measured.
Take refinery, Jinxi RFCC gasoline as raw material, carry out hydrodesulfurization performance and the evaluation of olefin saturated performance of catalyst.The catalytic reaction temperature is 280 ℃, reaction pressure 3.0MPa, liquid hourly space velocity (LHSV) 2h
-1, hydrogen-oil ratio 600(volume ratio) under hydrodesulfurization and olefin saturated performance result as follows.
As can be seen from the above table, it is selective that catalyst of the present invention has preferably hydrodesulfurization.Al with routine
2O
3Catalyst is compared, and catalyst of the present invention is restrained absorption and the hydrogenation saturated reaction of alkene, has improved the desulfuration selectivity of catalyst to gasoline.
Claims (5)
1. preparation method who is used for the gasoline hydrodesulfurizationmethod catalyst is characterized in that comprising:
(1) preparation of Mg-Al composite oxide carrier: a certain amount of magnesium nitrate and aluminum nitrate are dissolved in ionized water, under certain hydrolysis temperature and stirring, with the pH value conditioning agent pH value of solution is adjusted in PH9-10, under constant temperature, obtain white pasty state precipitation behind the hydrolysis, then crystallization refluxes under certain crystallization temperature, precipitation after the crystallization is 120 ℃ of lower dry 10 h after washing, and dried product is namely being obtained the Mg-Al composite oxide carrier after the roasting under certain sintering temperature;
(2) preparation of catalyst: take the mixed solution of isopyknic cobalt nitrate and ammonium molybdate as maceration extract, at room temperature with maceration extract and carrier hybrid infusion 4 h, 120 ℃ of drying 5 h, again in 500 ℃ of roasting 3 h, through getting the particle of particle diameter 3.0mm～4.0 mm after grinding, namely get gasoline hydrodesulfurizationmethod catalyst of the present invention.
2. the preparation method of catalyst as claimed in claim 1 is characterized in that the hydrolysis temperature described in the described step (1) is 70-90 ℃, and crystallization temperature is 60-80 ℃, and sintering temperature is 500-600 ℃.
3. the preparation method of catalyst as claimed in claim 1 is characterized in that the pH value conditioning agent described in the described step (1) is NaOH, potassium hydroxide, ammonia spirit.
4. such as the preparation method of claim 1 or 2 or 3 described catalyst, it is characterized in that the mass ratio of magnesium nitrate described in the described step (1) and aluminum nitrate is 8-12:1;
The amount ratio of maceration extract and carrier is 2-4:1 described in the step (2).
5. the preparation method of catalyst as claimed in claim 1, it is characterized in that the hydrolysis temperature described in the described step (1) is 80 ℃, crystallization temperature is 70 ℃, sintering temperature is 550 ℃, the pH value conditioning agent is ammonia spirit, the mass ratio of magnesium nitrate and aluminum nitrate is 10:1, and the amount ratio of maceration extract and carrier is 3:1 described in the step (2).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106512984A (en) * | 2016-12-14 | 2017-03-22 | 福州大学 | Preparation method of high-activity diesel hydrodesulfurization catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106512984A (en) * | 2016-12-14 | 2017-03-22 | 福州大学 | Preparation method of high-activity diesel hydrodesulfurization catalyst |
| CN106512984B (en) * | 2016-12-14 | 2019-09-13 | 福州大学 | A kind of preparation method of high activity diesel hydrogenation for removal sulphur catalyst |
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Application publication date: 20130213 |